UNIVERSITY  OF  CALIFORNIA  PUBLICATIONS 

COLLEGE  OF  AGRICULTURE 

AGRICULTURAL  EXPERIMENT  STATION 

BERKELEY,  CALIFORNIA 


PHENOLIC  INSECTICIDES  AND 
FUNGICIDES 


BY 

GEO.  P.  GRAY 


BULLETIN  No.  269 

Berkeley,  Calif.,  April,  1916 


UNIVERSITY   OF  CALIFORNIA  PRESS 

BERKELEY 

1916 


Benjamin  Ide  Wheeler,  President  of  the  University. 
EXPERIMENT    STATION    STAFF 

HEADS   OP  DIVISIONS 

Thomas  Forsyth  Hunt,  Director. 

Edward  J.  Wickson,  Horticulture   (Emeritus). 

Herbert  J.  Webber,  Director  Citrus  Experiment  Station;  Plant  Breeding. 

Hubert  E.  Van  Norman,  Vice-Director;   Dairy  Management. 

William  A.  Setchell,  Botany. 

Myer  E.  Jaffa,  Nutrition. 

Robert  H.  Loughridge,  Soil  Chemistry  and  Physics   (Emeritus). 

Charles  W.  Woodworth,  Entomology. 

Ralph  E.  Smith,  Plant  Pathology. 

J.  Eliot  Coit,  Citriculture. 

John  W.  Gilmore,  Agronomy. 

Charles  F.  Shaw,  Soil  Technology. 

John  W.  Gregg,  Landscape  Gardening  and  Floriculture. 

Frederic  T.  Bioletti,  Viticulture  and  Enology. 

Warren  T.  Clarke,  Agricultural  Extension. 

John  S.  Burd,  Agricultural  Chemistry. 

Charles  B.  Lipman,  Soil  Chemistry  and  Bacteriology. 

Clarence   M.   Haring,  Veterinary  Science   and   Bacteriology. 

Ernest  B.  Babcock,  Genetics. 

Gordon  H.  True,  Animal  Husbandry. 

James  T.  Barrett,  Plant  Pathology. 

Fritz  W.  Woll,  Animal  Nutrition. 

A.  V.  Stubenrauch,  Pomology. 

Walter  Mulford,  Forestry. 

W.  P.  Kelley,  Agricultural  Chemistry. 

H.  J.  Quayle,   Entomology. 

D.  T.  Mason,  Forestry. 

J.  B.  Davidson,  Agricultural  Engineering. 

Elwood  Mead,  Rural  Institutions. 

H.  S.  Reed,  Plant  Physiology. 

William  G.  Hummel,  Agricultural  Education. 

Leon  M.  Davis,  Dairy  Industry. 

John  E.  Dougherty,  Poultry  Husbandry. 

S.  S.  Rogers,  Olericulture. 

Frank  Adams,  Irrigation  Practice. 

David  N.  Morgan,  Assistant  to  the  Director. 

Mrs.  D.  L.  Bunnell,  Librarian. 

division  of  entomology 

C.  W.  Woodworth  E.  O.  Essig 

W.  B.  Herms  S.  B.  Freeborn 

E.  C.  Van  Dyke  E.  P.  Van  Duzee 

Geo.  A.  Coleman  M.  R.  Miller 

Geo.  P.  Gray  E.  R.  de  Ong 


INTRODUCTION 

This  bulletin  is  a  report  of  such  examinations  and  analyses  as  were 
made  of  the  samples  of  phenolic  insecticides  and  fungicides  collected 
during  the  fiscal  years  July  1,  1911,  to  June  30,  1913,  with  comments, 
description  of  methods  of  examination  and  information  concerning 
these  products  that  seem  of  interest.  The  work  was  done  under  the 
authority  of  the  California  Insecticide  Law  of  1911  (California 
Statutes  of  1911,  Chapter  653). 

Part  I  is  a  general  discussion  of  phenolic  insecticides  and  fungi- 
cides, classification  of  the  materials  found  on  the  market,  description, 
properties  and  uses  of  the  refined  phenols  in  common  use,  description, 
properties  and  uses  of  the  crude  phenols  and  compounded  remedies. 

The  especial  points  brought  out  in  the  discussion  are : 

(1)  All  of  the  cresols  are  more  active  fungicides  than  phenol,  the 
higher  boiling  cresols  (especially  meta-cresol)  are  more  active  as 
fungicides  than  the  lower-boiling  cresols. 

(2)  Commercial  cresol  is  usually  a  mixture  of  the  three  cresols. 

(3)  A  specially  prepared  high-boiling  cresol  would  be  of  par- 
ticular value  in  the  preparation  of  disinfectants. 

(4)  "Coal-tar  Creosote,"  "Crude  Carbolic  Acid,"  and  "Creosote 
Oil"  are  practically  synonymous  terms  as  commercially  used  in  the 
United  States.  The  general  term  "Crude  Phenols"  is  applied  to  the 
above  in  the  author's  classification.  Large  quantities  of  the  mixed 
residues  from  all  sorts  of  tars  are  sold  under  the  above  names,  as  well 
as  under  the  names  of  many  proprietary  Lice-killers,  etc. 

(5)  It  is  thought  that  the  use  of  the  word  "Creosote"  should  be 
restricted  to  the  phenol-bearing  distillates,  heavier  than  water,  ob- 
tained by  the  distillation  of  a  tar  or  a  tar-like  substance.  So-called 
"Oil-tar  Creosote,"  if  the  above  is  correct,  is  an  adulterant  when 
added  to  crude  phenols,  and  is  a  substitute  when  sold  in  place  of  them. 

(6)  Crude  Cresylic  Acid  is  a  more  appropriate  term  to  be  applied 
to  the  liquid  commonly  sold  as  Crude  Carbolic  Acid,  with  emphasis  on 
the  word  "Crude."  The  source  of  the  crude  phenols  should  be  re- 
stricted to  the  light  oils,  designating  the  phenol-bearing  heavy  oils  as 
creosotes. 

(7)  Dependable  phenolic  insecticides  and  fungicides,  especially 
the  soluble  and  emulsifiable  ones,  possess  many  distinct  features  of 
advantage  over  other  materials  used  for  the  same  purpose.  If  products 
of  this  sort  and  the  crude  materials  from  which  they  are  made  could 

[329] 


330  UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 

be  standardized  and  supplied  of  reasonable  uniformity  from  season 
to  season,  it  is  thought  that  they  might  be  extended  to  a  far  wider 
field  of  usefulness  than  at  present. 

Part  II  is  a  classification  of  the  samples  examined  and  a  tabulation 
of  the  results  of  the  determination  of  their  phenolic  contents,  with 
comments. 

From  the  results  of  examination  of  the  176  samples  listed  in  the 
tables  and  a  study  of  the  situation,  the  following  conclusions  and  ob- 
servations are  made  concerning  such  materials  as  are  offered  for  sale 
in  the  state : 

(1)  The  refined  phenols  are  of  good  quality. 

(2)  A  very  unsatisfactory  condition  exists  in  regard  to  the  crude 
phenols.  The  amount  of  phenols  found  in  the  samples  analysed  varied 
from  4.9  to  38.4  per  cent.  A  variation  of  15  to  18  per  cent,  from  the 
amount  of  phenols  stated  on  the  label  is  a  matter  of  frequent  oc- 
currence. 

(3)  The  phenols  are  not  necessarily  the  most  active  insecticidal 
constituents  of  the  non-em ulsifiable  preparations  but  are  probably  the 
most  active  as  fungicides.  Analyses  of  the  samples  of  this  group  indi- 
cate a  decided  opportunity  for  improvement. 

(4)  The  emulsifiable  preparations  made  up  with  fatty  soap  emulsi- 
fier  are  fairly  satisfactory  in  conforming  to  guarantee,  although  the 
variation  in  total  phenols  is  rather  remarkable,  ranging  from  4.1  per 
cent,  to  71.86  per  cent. 

(5)  The  emulsifiable  preparations  made  up  similar  to  the  above 
but  containing  rosin  soap  or  a  mixed  rosin  and  fatty  soap,  most  fre- 
quently known  as  ' '  carbolic  sheep  dips, ' '  is  the  group  with  the  greatest 
number  of  representatives.  In  these  the  phenolic  content  varied  from 
3.8  per  cent,  to  25.2  per  cent.  Of  the  dips  stating  percentages  of  active 
ingredients,  more  than  one  third  were  not  within  5  per  cent,  of  the 
guarantee.  This  state  of  affairs  indicates  the  need  of  a  more  accurate 
knowledge  of  the  composition  of  the  products  on  the  part  of  some  of 
the  manufacturers. 

(6)  The  soluble  preparations  of  the  type  represented  by  the  Liquor 
Cresolis  Compositus  of  the  U.  S.  Pharmacopoeia  are  fairly  reliable  in 
conforming  to  the  guarantee  of  phenols. 

(7)  Manufacturers  and  dealers  are  not  accused  of  wilfully  making 
or  selling  low-grade  or  non-standard  products,  but  it  appears  that 
material  has  often  been  guaranteed  and  sold  with  but  slight  knowledge 
of  its  composition.  The  blame  must  be  shared  with  the  producers  of 
the  raw  materials  who  have  shown  great  hesitancy  in  giving  specific 
guarantees  for  their  output. 


PHENOLIC    INSECTICIDES    AND    FUNGICIDES  331 

(8)  Amendments  to  the  Insecticide  Law  have  done  away  with  the 
requirement  of  stating  the  percentage  of  active  ingredients  in  an  in- 
secticide or  fungicide.  This  lends  encouragement  to  the  promoter  of 
worthless  or  non-standard  proprietary  preparations  and  the  sellers 
of  heterogeneous  by-products  of  uncertain  composition.  The  most 
serious  result  of  the  amendments  is,  however,  that  the  accomplishment 
of  the  standardization  of  insecticides  and  fungicides,  so  much  to  be 
desired  by  the  consumer  and  the  conscientious  producer,  is  greatly 
impeded. 

Part  III  describes  qualitative  methods  most  frequently  used  in 
the  Insecticide  Laboratory  for  the  examination  of  phenolic  insecticides 
and  fungicides,  and  gives  references  to  methods  for  their  complete 
examination  which  are  in  use  by  the  U.  S.  Department  of  Agriculture. 
Apparatus  used  in  the  determination  of  total  phenols  by  Chapin's 
method  is  illustrated,  including  some  new  apparatus  and  conveniences 
developed  during  the  progress  of  the  work. 

An  index  of  samples  is  appended  giving  the  laboratory  number 
of  each  compounded  and  proprietary  remedy  examined  and  the  table 
in  which  listed.  The  different  names  applied  to  the  crude  and  refined 
phenols  are  also  indexed,  showing  the  number  of  the  table  in  which 
the  material  is  listed.  The  headings  of  the  tables  referred  to  are  made 
to  correspond  to  the  classification  suggested  in  Part  I,  so  that  the 
author's  classification  of  any  particular  sample  may  be  readily 
ascertained. 


PHENOLIC  INSECTICIDES  AND  FUNGICIDES 

By  GEO.  P.  GRAY 


Part  I 
GENERAL  DISCUSSION 

PAGE 

Quality  of  Standard  Insecticides  and  Fungicides  332 

Quality  of  Phenolic  Insecticides  and  Fungicides  ! 333 

Active  Ingredients 333 

Definitions    333 

Classification 334 

Refined  Phenols,  Description  and  Properties  335 

Phenol  335 

Cresol  335 

Uses  of  the  Refined  Phenols  336 

Crude  Phenols,  Description  and  Properties 337 

Uses  of  the  Crude  Phenols  339 

Compounded  and  Proprietary  Remedies  339 

Uses  of  the  Emulsifiable  Phenolic  Liquids  344 

This  bulletin  is  a  report  of  such  examination  and  analyses  as  were 
made  of  the  samples  of  phenolic  insecticides  and  fungicides  collected 
during  the  fiscal  years,  July  1,  1911,  to  June  30,  1913,  with  com- 
ments, description  of  methods  of  examination  and  information  con- 
cerning these  products.  The  samples  were  taken  by  authorized  depu- 
ties of  the  Director  of  the  Agricultural  Experiment  Station  of  the 
University  of  California  and  examined  in  the  Insecticide  Laboratory 
acting  under  the  authority  of  the  California  Insecticide  Law  of  1911 
(California  Statutes  of  1911,  Chapter  653). 

Not  all  of  the  samples  collected  have  been  analyzed  on  account  of 
duplication  and  the  small  size  of  some  of  the  samples.  It  is  thought, 
however,  that  a  sufficient  number  have  been  analyzed  to  fairly  repre- 
sent this  class  of  insecticides  and  fungicides  offered  for  sale  in  the 
state  during  the  period  of  inspection. 

QUALITY  OF  STANDARD  INSECTICIDES  AND  FUNGICIDES 
The  standard  and  more  important  insecticides  and  fungicides  in 
general  use  in  the  state  are  the  arsenicals,  cyanides,  sulfur  and  sulfur 
compounds,  petroleum  oils,  tobacco  preparations,  and  Bordeaux  mix- 
ture.   With  comparatively  few  exceptions,  the  above  have  been  found 

[332] 


PHENOLIC   INSECTICIDES   AND    FUNGICIDES  333 

to  be  free  from  adulteration,  and  it  is  believed  that  the  consumers  of 
the  state  are  being  supplied  with  materials  of  worth  and  reliability. 
This  is  particularly  true  of  the  arsenicals,  due  no  doubt  in  part  to 
the  fact  that  the  Federal  Insecticide  Law  of  1910  fixes  a  standard  for 
lead  arsenate  and  Paris  green,  that  California  has  had  in  operation 
a  Paris  green  law  since  1901,  and  that  this  station  has  been  particu- 
larly active  in  the  investigation  of  the  composition  and  suitability  of 
other  arsenicals. 

QUALITY  OF  PHENOLIC  INSECTICIDES  AND  FUNGICIDES 

It  is  to  be  regretted  that  similarly  favorable  comment  cannot  be 
made  upon  many  of  the  insecticides  and  fungicides  listed  in  this  bulle- 
tin, more  especially  upon  the  crude  materials.  Preliminary  examina- 
tion of  the  samples  of  the  latter  class  of  substances  showed  wide  varia- 
tions in  composition  in  some  cases,  in  which  to  all  appearances  the 
materials  were  alike  and  bore  similar  names.  Consequently,  samples 
were  obtained  from  wholesale  and  retail  dealers  in  different  parts  of 
the  state  for  analysis.  This  collection  contained  so  many  different 
brands  that  complete  analyses  were  not  attempted.  Attention  was 
given  to  qualitative  tests  to  indicate  the  nature  of  the  substance  and 
to  quantitative  determination  of  the  total  phenols  (or  tar  acids) 
present.  (Description  of  methods  of  examination  are  given  in  Part 
III  of  this  bulletin). 

ACTIVE  INGREDIENTS 

It  is  not  contended  that  the  phenols  are  the  only  active  ingredients 
of  this  class,  as  indeed  the  oils,  naphthalene,  anthracene,  pyridin,  etc., 
have  decided  value  in  destroying  or  repelling  insects.  It  is  thought, 
however,  that  the  phenols  are  the  most  active  and  are  undoubtedly 
the  most  valuable  in  a  commercial  way,  so  that  if  any  constituent  is 
below  guarantee,  this  is  likely  to  be  the  one  for  commercial  reasons. 

DEFINITIONS 
The  Phenols 

This  name  is  given  to  a  certain  group  of  organic  substances  other- 
wise known  as  the  hydroxyl  derivatives  of  the  benzene  series.  The 
simplest  phenol  is  known  as  phenol  or  carbolic  acid.  Other  phenols 
are  of  common  occurence  and  are  collectively  known  as  the  phenols, 
the  group  taking  its  name  from  the  simplest  member  of  the  group. 

When  the  word  "phenol"  is  used  in  the  singular  without  qualifi- 
cation, the  definite  chemical  substance  (C6H5OH),  or  hydroxyben- 
zene,   commonly   called   carbolic   acid,   is   meant.     When   the   word 


334  UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 

"phenols"  (plural)  is  used,  the  phenol  group  is  meant,  spoken  of  in 
commercial  language  as  "tar  acids." 

CLASSIFICATION 

Considerable  confusion  exists  in  the  nomenclature  of  the  phenols 
in  general,  and  of  phenolic  insecticides  and  fungicides  in  particular. 
The  names  of  definite  chemical  substances  are  often  confused  with 
familiar  trade  names  of  compounded  preparations.  Even  pharmacists 
have  sold  to  inspectors  of  this  office  compounded  articles  under  the 
definite  name  of  one  of  the  phenols. 

In  order  to  clear  up  some  of  these  points,  a  tentative  classification 
of  the  phenolic  insecticides  and  fungicides,  so  far  as  known  to  this 
office,  is  suggested  below.  Comments  are  solicited  by  interested 
parties,  suggesting  changes  or  additions  that  may  seem  advisable. 
Following  this  is  given  a  more  detailed  description  of  the  different 
substances  with  information  concerning  their  derivation  or  compound- 
ing, and  uses. 

In  a  preliminary  examination  of  the  compounded  and  proprietary 
remedies  they  were  separated  into  classes  arranged  according  to  the 
table  as  given  below.  The  classification  of  any  particular  compound 
listed  in  this  bulletin  may  be  ascertained  by  reference  to  the  index 
of  samples,  which  gives  the  sample  number  and  the  table  in  which  it 
is  listed.1 

CLASSIFICATION  OF  PHENOLIC  INSECTICIDES  AND  FUNGICIDES 

I.  Eefined  Phenols: 

1.  Phenol.      (C6H5OH).      Commonly    called    Carbolic   Acid,    and    occasionally 

called  Phenic,  or  Phenylic  Acid. 
Chemically  known   as   Hydroxybenz-ene    (or   -ol),   Benzo-phenol,   or   Phenyl 
Hydroxide. 

2.  Cresol.      (C6H4CH3OH).      (Ortho,   meta,   para  and   mixtures).      Commonly 

called  Cresylic  Acid  or  Kresylic  Acid,  and  occasionally  called  Kresol 
or  Cresylol. 
Chemically  known   as  Hydroxytolu-ene    (or  -ol),  or  Methylhydroxybenz- 
ene  (or  -ol). 

3.  Higher  Phenols. 

II.  Crude  Phenols: 

1.  Coal-tar  Creosote  ]  Commercial  terms  applied  to  mixed  re- 

2.  Creosote  Oil  j>        sides  from  tar  refineries  containing 

3.  Crude  Carbolic  Acid    I         variable  amounts  of  phenols. 

4.  Wood-tar  Creosote  (infrequently  used  as  an  insecticide). 


i  The  classification  of  the  emulsifiable  liquids  may  not  be  strictly  accurate 
in  respect  to  the  soap  employed,  as  many  of  these  contain  a  mixture  of  fatty 
and  rosin  soap.  If  a  good  test  for  rosin  was  obtained,  the  compound  was 
placed  in  the  rosin  soap  class;  if  the  test  was  negative  or  faint,  it  was  placed 
in  the  fatty  soap  class. 


PHENOLIC    INSECTICIDES    AND    FUNGICIDES  335 


III.  Compounded  and  Proprietary  Remedies: 

1.  Liquids 

A.  Insoluble  in  water 

(a)  Non-emulsifiable 

(1)  With  Tar  Oil  Solvent 

(2)  With  Petroleum  Solvent 

(3)  Mixtures  of  (1)  and  (2) 

(b)  Emulsifiable 

(1)  With  Fatty  Soap  Emulsifier 

(2)  With  Rosin  Soap  Emulsifier 

(3)  With  Mixed  Soap  Emulsifier 

B.  Soluble  in  Water 

2.  Solids  and  Semi-solids 

A.  Ointments 

B.  Powders 

C.  Soaps. 


REFINED  PHENOLS 

The  phenols  in  most  common  use  as  insecticides  and  fungicides  are 
phenol  and  cresol.  A  discussion  of  the  properties  and  composition  of 
these  two  can  be  found  in  any  work  on  organic  chemistry.  A  few 
words  on  this  topic  may  not  be  out  of  place  at  this  time. 

Phenol  or  Carbolic  Acid 

Phenol  when  in  a  pure  state  is  a  white  solid  at  ordinary  tempera- 
tures, forming  long  needle-shaped  crystals  when  crystallized  from  a 
suitable  solvent.  It  melts,  however,  at  a  temperature  slightly  above 
42°  C.  (108°  F.)  so  that  on  a  very  hot  day  it  will  be  a  liquid.  A 
small  amount  of  moisture  or  cresol  lowers  the  melting  point  so  that 
as  purchased  it  is  in  liquid  form  unless  very  pure.  The  solid  absorbs 
moisture  from  the  air  and  under  the  combined  influence  of  air,  light, 
and  moisture,  it  often  turns  to  a  reddish  or  pink  color. 

Cresol  or  Cresylic  Acid 

The  most  evident  physical  property  distinguishing  cresol  from 
phenol  is  that  cresol  is  a  liquid  at  ordinary  temperatures  while  phenol 
is  a  solid.  The  odor  of  cresol  is  somewhat  like  that  of  phenol  and  is 
not  at  all  unpleasant.  There  are  three  kinds  of  cresols,  known  as 
ortho,  meta,  and  para  cresol,  commercial  cresol  being  a  mixture  of 
the  three.  Their  separation  would  be  a  difficult  commercial  operation, 
possibly  excepting  the  partial  separation  of  ortho  cresol  which  has  a 
lower  boiling  point  than  the  others. 


336  UNIVERSITY   OP    CALIFORNIA — EXPERIMENT    STATION 

USES  OF  THE  BEFINED  PHENOLS 

Phenol 

The  principal  use  of  phenol  pertinent  to  the  topic  is  as  an  anti- 
septic and  disinfectant,  although  its  use  as  such  is  somewhat  limited 
on  account  of  the  difficulty  of  making  a  uniform  mixture  with  water, 
its  poisonous  nature,  and  causticity.  The  Cresols  have  been  found  to 
be  more  efficient,  less  poisonous,  and  less  caustic,  although  less  soluble 
in  water.  The  solubility  defect  has  been  remedied  by  the  use  of  the 
soluble  and  emulsifiable  preparations  described  on  succeeding  pages. 

Solutions  of  phenol  in  kerosene  or  other  solvent  are  on  the  market 
as  proprietary  compounds. 


Cresol 

Cresol  is  the  active  and  most  valuable  germicidal  constituent  of 
the  crude  phenols  and  is  usually  the  only  representative  of  the  phenol 
family  to  be  found  in  any  considerable  quantity  in  crude  carbolic 
acid  and  creosote. 

It  is  used  to  fortify  the  compounded  phenolic  preparations  which 
have  been  made  from  the  crude  phenols.  It  is  also  used  in  the  prepara- 
tion of  the  higher  grade  soluble  and  emulsifiable  "dips"  and  disin- 
fectants. 

It  is  used  quite  extensively  as  an  ingredient  in  the  preparation  of 
ointments,  salves,  and  in  antiseptic  and  insecticidal  soaps. 

More  recently  cresol  finds  a  very  useful  field  in  the  preparation  of 
emulsifiers  for  the  various  petroleum  oils  to  be  used  as  insecticide 
sprays.  It  is  used  as  a  necessary  ingredient  in  making  up  the  more 
satisfactory  "miscible  oils."  The  formula  given  by  Penny2  for  the 
preparation  of  his  emulsifier  or  "soap  solution"  calls  for  the  use  of 
"carbolic  acid,"  the  grade  known  as  "Liquid  crude,  one  hundred  per 
cent,  straw  color."  The  preceding  commercial  term  is  rather  mis- 
leading, as  one  not  familiar  with  commercial  language  might  infer 
a  product  essentially  carbolic  acid  of  great  purity.  As  a  matter  of 
fact,  this  commodity  is  only  a  very  good  grade  of  mixed  phenols  and 
sometimes  may  be  very  largely  cresol.  This  grade  of  ' '  carbolic  acid, ' ' 
however,  has  been  found  by  Penny  to  be  satisfactory  in  the  prepara- 
tion of  a  great  variety  of  miscible  oils. 

Many  liquid  soaps  are  now  on  the  market,  some  of  which  contain 
as  high  as  twenty-five  per  cent,  cresol. 


2  Del.  Agr.  Exp.  Sta.,  Bull.  75,  p.  7,  1906. 


PHENOLIC   INSECTICIDES    AND    FUNGICIDES  337 

CRUDE  PHENOLS 

There  appears  to  be  no  very  definite  distinction  between  the  pro- 
ducts sold  under  the  names  of  coal-tar  creosote,  creosote  oil,  and  crude 
carbolic  acid.  Sadtler3  expresses  the  situation  thus:  "The  name 
'Kreosot'  was  first  applied  by  Reichenbach,  in  1832,  to  the  character- 
istic antiseptic  principle  contained  in  wood-tar  (C.  Rice,  Amer.  Journ. 
Pharm.,  1894,  167).  Carbolic  acid  was  discovered  soon  after  by 
Runge  in  coal-tar,  and  was  long  confused  with  the  wood-tar  principle : 
and  the  crude  carbolic  acid  from  coal-tar  is  still  known  as  'Coal-tar 
creosote.'  Somewhat  similar  products  are  now  obtained  from  other 
sources,  so  that  much  confusion  has  arisen.  The  term  '  creosote '  when 
used  without  qualification,  ought  to  be  understood  as  signifying  the 
product  from  wood-tar,  but  it  is  better  to  describe  Reichenbach 's  sub- 
stance as  'wood-tar  creosote,'  and  employ  the  unqualified  word  'creo- 
sote' in  a  generic  sense  as  meaning  the  mixed  phenols  and  phenoloid 
bodies  obtained  from  wood-tar,  coal-tar,  blast-furnace-tar,  shale-oil, 
bone-oil,  or  other  sources.  The  term  'creosote'  should  be  restricted 
to  the  phenolic4"  derivatives  from  the  above  or  similar  sources,  the 
crude  products  from  which  they  are  derived  being  the  corresponding 
'creosote  oils.' 

Coal-Tar  Creosote   Oil* 

"Coal-tar  creosote  oil  commonly  consists  of  that  portion  of  coal- 
tar  which  distills  between  200°  and  300°,  together  with  the  residual 
oils  from  the  manufacture  of  crude  carbolic  acid,  naphthalene,  and 
anthracene.  This  description,  however,  applies  especially  to  the  best- 
managed  works.  In  some  works  every  residue  which  cannot  be  used 
for  any  other  purpose  finds  its  way  into  the  creosote  oil  well." 

The  manufacturers'  agents  admit  that  insofar  as  trade  usage  is 
concerned,  there  is  no  well  defined  distinction  between  the  products 
commonly  sold  under  the  names  Coal-tar  Creosote,  Creosote  Oil,  and 
Crude  Carbolic  Acid.  In  some  cases,  however,  there  seems  to  be  this 
distinction:  the  crude  carbolic  acid  may  have  been  derived  from  a 
certain  fraction  resulting  from  the  distillation  of  coal-tar  which  is 
lighter  than  water  and  therefore  may  contain  a  greater  proportion 
of  the  lighter  oils  than  the  creosote  oils  which  may  have  been  ob- 
tained from  the  fractions  which  are  heavier  than  water. 


s  Allen 's  Commercial  Organic  Analysis,  4th  Ed.,  Vol.  Ill,  346. 
4  Italics  by  the  author. 
*  Loc.  cit.,  page  365. 


338  UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 

It  is  believed  that  the  above  is  the  only  distinction  which  is  made, 
but  this  distinction  would  not  be  applicable  to  products  from  works 
described  by  Sadtler  in  which  "every  residue  which  cannot  be  used 
for  any  other  purpose  finds  its  way  into  the  creosote  oil  well. ' ' 

The  Forest  Service  of  the  United  States  Department  of  Agricul- 
ture has  made  an  extended  study  of  commercial  creosotes  and  a  circu- 
lar has  been  issued  giving  a  summary  of  the  work  up  to  1912.5  In 
this  circular  definitions  and  terms  are  suggested  in  order  to  differen- 
tiate between  the  various  creosotes.  The  general  term  "creosote"  is 
defined  as  "  a  distillate  heavier  than  water  obtained  by  the  distillation 
of  a  tar  or  a  tar-like  substance."  The  term  "oil-tar  creosote"  is  in- 
cluded in  the  definitions  and  is  the  only  one  to  which  exception  might 
be  taken.  While  the  meaning  is  perfectly  clear  to  those  conversant 
with  the  subject,  it  is  thought  that  the  word  "creosote"  applied  to 
such  a  product  is  misleading.  In  fact  this  oil-gas  tar  distillate  does 
not  appear  to  be  entitled  to  the  name  "creosote"  at  all,  for  the  rea- 
son that  the  phenols  and  phenoloid  bodies  are  entirely  lacking  in  the 
tars  produced  from  oil.  The  phenol  group  is  held  to  be  an  essential 
and  characteristic  antiseptic  principle  of  all  creosotes.  Some  such 
term  as  "oil-tar  distillate"  would  seem  to  be  more  appropriate. 

Crude  Carbolic  Acid 

There  can  be  no  place  for  the  continued  use  of  this  term  except 
out  of  respect  for  old  age.  It  is  a  matter  of  common  knowledge,  to 
those  who  have  looked  into  the  question,  that  "crude  carbolic  acid1' 
contains  no  carbolic  acid  (phenol),  or  at  most  only  a  trace.  The  only 
phenols  present  are  cresylic  acid  (cresol)  and  the  higher  phenols. 
This  commodity,  as  commonly  sold  in  this  state,  and  doubtless  else- 
where, may  be  more  properly  referred  to  as  "  crude  cresylic  acid. ' ' 

As  expressed  by  one  of  the  manufacturers'  agents  dealing  in  creo- 
sotes, if  the  prospective  customer  is  interested  in  a  liquid  for  use  as 
a  shingle  stain  or  wood  preservative,  he  asks  for  creosote  and  creosote 
is  sold  to  him.  If  the  customer  desires  to  disinfect  his  premises  or 
rid  his  poultry  of  vermin,  he  asks  for  crude  carbolic  acid  and  obtains 
the  latter.    But  it  all  comes  out  of  the  same  tank ! 

It  is  perfectly  evident  that  in  many  cases  the  temptation  to  sell 
under  one  name  or  other  as  a  crude  phenol  ' '  every  residue  which  can- 
not be  used  for  any  other  purpose"  is  too  great  to  be  overcome.  And 
this  uncertain  and  variable  mixture,  whether  good  or  bad,  in  its 
original  form,  or  after  "doctoring,"  masquerades  under  hundreds  of 


s  Winslow,  C.  P.,  U.  S.  D.  A.  Forest  Service,  Circ.  206,  1912. 


PHENOLIC    INSECTICIDES    AND    FUNGICIDES  339 

fanciful  names  and  finally  falls  into  the  hands  of  the  unsuspecting 
consumer. 

USES  OF  THE  CRUDE  PHENOLS 
As  a  Fungicide 

According  to  the  Forest  Service  of  the  United  States  Department 
of  Agriculture,6  "By  far  the  largest  consumption  of  creosote  in  this 
country  is  in  the  treatment  of  wood  to  prevent  the  development  of 
wood-destroying  fungi.  In  1910  approximately  63,266,271  gallons  of 
creosote  was  used  in  the  United  States  for  this  purpose  of  which 
18,184,355  gallons  was  of  domestic  production  and  45,081,916  gallons 
imported. ' ' 

The  use  of  creosote  as  indicated  ahove  clearly  establishes  its  status 
as  a  fungicide  and  hence  it  comes  under  the  supervision  of  the  Cali- 
fornia Insecticide  and  Fungicide  Law  of  1911. 

Little  attention,  however,  has  been  given  to  this  phase  of  the  sub- 
ject, but  it  may  properly  become  one  of  the  activities  of  the  Insecti- 
cide Laboratory  in  the  future. 

As  a  Disinfectant 
Large  quantities  of  the  crude  phenols  are  annually  consumed  as  a 
general  disinfectant  about  drains,  closets,  cesspools,  and  the  like,  and 
in  the  disinfection  of  stables.  Their  use  for  this  purpose  is  being  dis- 
continued to  a  large  extent  in  favor  of  the  more  refined  products,  as 
the  crude  materials  have  been  found  to  be  so  unreliable. 

As  an  Insecticide 

They  are  also  used  quite  extensively  for  the  destruction  of  lice  and 
vermin  in  poultry  houses  and  stables,  in  this  case  being  sold  as  crude 
carbolic  acid,  but  perhaps  more  frequently  under  a  trade  name  as  a 
' '  Lice  Killer, ' '  containing  some  added  substance  such  as  carbon  bisul- 
fide and  very  often  a  petroleum  oil. 

Another,  and  perhaps  the  largest  market  aside  from  the  wood- 
preserving  industry,  is  in  the  preparation  of  the  so-called  carbolic 
sheep  dips  and  similarly  prepared  disinfectants. 

COMPOUNDED   AND  PKOPRIETARY  EEMEDIES 
Non-Emulsifiable  Liquids;  Insoluble  in  Water  (III-l-Aa) 
This  group  is  of  lesser  importance  than  those  following,  although 
the  number  of  brands  listed  is  fully  as  great. 

As  indicated  in  the  outline  of  classification,  this  group  has  been 
found  to  consist  of  three  subdivisions,  depending  upon  the  kind  of 
solvent  or  vehicle. 


G  Forest  Service  U.  S.  Department  of  Agriculture,  Circ.  206. 


340  UNIVERSITY    OF    CALIFORNIA- —EXPERIMENT    STATION 

1.  With  Tar  Oil  Solvent. 

Many  of  these  compounds  appear  to  be  by-products  of  oil  refineries 
and  some  of  these  might  be  classified  as  crude  phenols  except  for  their 
trade  names  which  bring  them  under  the  above  heading.  Certain 
mixtures  resulting  from  the  distillation  of  various  tars  are  often  sold 
as  insecticides  under  trade  names.  Carbon  bisulfide,  sulfur,  or  petro- 
leum distillates  are  sometimes  added  to  increase  their  ' '  strength ' '  and 
all-around  usefulness.  Naphthalene  is  usually  present  in  large  quanti- 
ties. Such  mixtures  as  these  are  best  known  as  "So  and  So's"  Lice 
Killer. 

Their  extended  use  and  the  number  of  brands  sold  in  the  state 
speak  well  of  their  value  as  lice  killers.  This  may  in  part  be  ac- 
counted for  by  the  fact  that  lice  and  mites  are  especially  susceptible 
to  the  action  of  oils  of  whatever  nature.  And  so  it  may  be  considered 
that  all  of  these  oils  are  of  value  in  the  destruction  of  vermin  that 
infest  animals.  When  the  phenols  are  present  in  appreciable  quanti- 
ties the  liquid  has  an  added  value  as  a  disinfectant.  This  constituent 
is  such  a  variable  quantity,  however,  that  great  reliance  cannot  be 
placed  in  them  as  disinfectants.  The  phenols  are  also  undoubtedly  of 
value  as  an  insecticide  if  present. 

2.  With  Petroleum  Solvent : 

A  number  of  brands  of  this  class  were  found  upon  the  market, 
widely  advertised  as  deodorizers,  insecticides,  and  disinfectants.  The 
principal  ingredient  of  most  of  these  is  kerosene,  in  which  varying 
quantities  of  phenol  are  dissolved.  The  solubility  of  phenol  in  kero- 
sene is  not  great  and  so  a  number  of  substances  such  as  benzene,  carbon 
tetra-chlorid,  etc.,  are  added  to  retain  the  phenol  in  solution.  Nitro- 
benzene (oil  of  mirbane)  is  almost  invariably  a  constituent  of  these 
mixtures  and  probably  has  value  as  an  insecticide  as  well  as  a  pleasant 
odor.  Some  contain  oil  of  citronella  which  is  a  repellent  to  insects  but 
to  man  has  a  pleasant  odor.  These  products  are  usually  clear  and 
transparent,  ranging  in  color  from  almost  colorless  to  a  light  brown. 

3.  Mixtures  of  1  and  2 : 

This  subdivision  has  been  added  to  accommodate  the  mixtures  of 
tar  oils  and  petroleum  oils,  the  first  consisting  for  the  most  part  of 
hydrocarbons  of  the  benzene  series  and  the  latter  of  hydrocarbons  of 
the  paraffin  series. 

Inasmuch  as  the  present  examination  of  the  phenolic  insecticides 
and  fungicides  is  concerned  chiefly  with  their  phenolic  content,  the 
analyses  of  the  non-emulsifiable  liquids,  insoluble  in  water,  were  not 
separately  tabulated  according  to  the  three  subdivisions  given  in  the 
classification,   but   are   all   given   in   one   table.     When   opportunity 


PHENOLIC    INSECTICIDES    AND    FUNGICIDES  341 

offers,  this  question  may  be  taken  up  more  fully  in  an  effort  to  classify 
the  liquids  of  this  group  according  to  their  respective  solvents. 

Emulsifiable  Liquids;  Insoluble  in  Water  (III-l-Ab) 

The  majority  of  the  emulsifiable  phenolic  liquids  are  produced 
from  the  crude  phenols  arid  therefore  contain  hydrocarbon  oils  chiefly 
of  the  benzene  series.  It  may  be  that  some  of  them  also  contain  oils 
from  petroleum  in  which  case  another  division  would  be  necessary. 
The  fact  was  not  evident  by  the  methods  used  and  hence  this  division 
is  not  made  in  the  classification.  The  only  distinction  made  was  on 
account  of  the  kind  of  soap  used  as  the  emulsifying  agent.  In  the 
examination  of  these  a  straight  rosin  soap  Avas  occasionally  indicated 
but  more  often  a  mixed  soap  of  rosin  and  fatty  acids  was  evident  as 
the  emulsifier.  A  smaller  proportion  was  found  in  which  rosin  was 
entirely  absent.  Pine  tar  is  used  as  an  ingredient  in  some  of  the 
dips  and  such  a  dip  would  give  a  test  for  rosin  and  the  soap  would  be 
classified  as  a  rosin  soap  if  the  pine  tar  were  present  in  sufficient 
quantity  to  give  a  good  test  for  rosin.  Those  compounds,  then,  classi- 
fied in  subdivision  1  of  this  group  with  rosin  soap  emulsifier  may  not 
all  belong  strictly  to  this  group,  but  many  should  come  in  a  third 
group  composed  of  those  compounds  in  which  a  mixture  of  rosin  and 
fatty  soap  is  the  emulsifying  agent.  This  group  will  accordingly  be 
discussed  as  a  whole  without  attempt  to  differentiate  between  the 
emulsifying  agent. 

Such  mixtures  are  most  often  spoken  of  as  ' '  Carbolic  Sheep  Dips, ' ' 
although  other  names  are  applied  when  intended  for  use  for  other 
purposes  than  for  the  dipping  of  sheep.  A  rosin  soap  or  a  mixture  of 
a  rosin  and  fatty  soap  is  thought  to  be  a  better  emulsifying  agent  than 
a  fatty  soap  alone — hence  the  greater  proportion  containing  rosin. 

For  the  sake  of  brevity  in  the  following  discussion,  the  compounds 
of  this  group  will  be  spoken  of  as  "dips." 

These  "dips"  may  be  made  by  first  combining  the  proper  amounts 
of  a  solution  of  lye  with  rosin  or  a  suitable  animal  or  vegetable  oil  or 
fat,  or  a  mixture  of  rosin  and  oil  or  fat,  to  form  a  liquid  soap.  There 
is  then  added  the  required  amount  of  crude  phenols  with  stirring  and 
heat.  (The  crude  phenols  may  have  been  purchased  under  the  name 
of  coal-tar  creosote,  creosote  oil,  or  crude  carbolic  acid). 

The  soap,  aided  by  the  phenols  present,  is  completely  dissolved  by 
the  coal-tar  oils  and  other  constituents  of  the  crude  phenols  at  the 
concentration  used  in  preparation.  There  results  a  homogeneous, 
thick,  dark  brown  fluid,  of  a  type  closely  allied  to  the  miscible  petro- 
leum oils  which  have  recently  come  into  the  market.     If  the  phenolic 


842  UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 

content  of  the  crude  phenols  is  insufficient  to  produce  a  finished  pro- 
duct of  the  desired  strength,  the  required  amount  of  pure  cresol  may 
be  added  during  the  process  in  order  to  bring  the  dip  up  to  mark  in 
respect  to  phenols. 

When  such  a  compound  is  diluted  with  water  the  oils  are  in  part 
thrown  out  of  solution,  but  immediately  form  an  emulsion  due  to  the 
action  of  the  soap  present.  These  emulsions  vary  in  color  from  almost 
milky  Avhite  to  a  brown,  reddish  or  greenish  color,  depending  upon 
the  composition  of  the  crude  materials  used  in  preparation. 

An  almost  perfect  emulsion  may  be  made  from  a  good  dip,  in  which 
the  oils  are  evenly  distributed  throughout  the  liquid  in  very  minute 
globules.  In  a  diluted  carefully  made  dip  no  oil  should  separate  from 
the  emulsion  and  rise  to  the  surface  except  after  prolonged  standing. 

Before  the  passage  of  regulatory  measures  by  the  Federal  Govern- 
ment and  by  some  of  the  states,  no  great  difficulty  was  experienced  in 
the  commercial  manufacture  and  sale  of  these  dips  and  disinfectants 
as  the  public  is  very  apt  to  judge  the  "strength"  of  such  a  compound 
by  the  vileness  of  its  odor  and  the  latter  quality  is  not  usually  lacking 
in  such  mixtures,  whether  efficient  or  valueless.  The  smell  of  a  prep- 
aration, however,  is  no  index  of  its  efficiency  as  an  insecticide  or 
fungicide. 

The  comparative  ease  of  manufacture  and  small  cost  of  such  com- 
pounds offer  a  convenient  and  lucrative  outlet  for  no  small  amount  of 
the  products  of  coal-tar  refineries  and  when  not  taken  advantage  of 
to  the  detriment  of  the  product  marketed,  has  been  a  source  of  great 
benefit  to  the  general  public.  A  dependable  dip  of  this  sort  possesses 
many  distinct  features  of  advantage  over  other  materials  used  for  the 
same  purposes. 

Liquids  Soluble  in  "Water.     (III-l-B) 

This  group  in  general  represents  a  higher  grade  and  more  ex- 
pensive product  than  the  former  and  a  group  of  more  definite  com- 
position. The  Liquor  Cresolis  Compositus  (Compound  Solution  of 
Cresol),  recognized  by  the  United  States  Pharmacopoeia  as  an  offi- 
cinal preparation,  may  be  taken  as  an  example  of  this  type.  This 
compound  is  composed  of  equal  parts  of  cresol  and  potash-linseed-oil 
soap.  Lysol  is  probably  the  most  widely  known  and  extensively  adver- 
tised proprietary  representative  of  this  group.  In  fact,  the  word 
lysol  is  often  confused  with  the  word  cresol. 

These  soluble  phenolic  compounds  have  the  great  advantage  of 
being  readily  soluble  in  water  and  usually  contain  a  high  percentage  of 


PHENOLIC    INSECTICIDES    AND    FUNGICIDES  343 

phenols,  usually  cresols.  They  are  preparations  very  similar  in  com- 
position to  the  officinal  preparation  with  perhaps  fish  oil  soap  present, 
instead  of  the  linseed  oil  soap  specified  in  the  former. 

This  group  is  characterized  by  the  absence  of  the  tar  oils,  pure 
cresol  being  used  in  their  preparation.  Cresol  and  the  other  phenols 
are  acted  upon  by  the  alkalies  forming  compounds  which  are  soluble 
in  water,  so  that  when  a  compound  of  this  nature  is  diluted  with 
water,  there  is  no  oil  to  be  freed  and  emulsified  by  the  soap. 

McBryde7  has  made  a  study  of  this  class  of  compounds  and  con- 
cludes that 

"(1)  Liquor  cresolis  compositus  is  strongly  germicidal  for  the  following 
micro-organisms:  Bacillus  pyocyaneus,  B.  cholerae  suis,  B.  coli  communis,  B.. 
typhosus,  B.  tuberculosis,  and  Staphylococcus  pyogenes  aureus. 

"(2)  The  germicidal  efficiency  of  liquor  cresolis  compositus  increases  with 
the  boiling  point  of  the  cresol  it  contains,  and  solutions  of  liquor  cresolis 
compositus  made  from  the  higher-boiling  cresols — i.e.,  cresols  which  approxi- 
mate paracresol  and  metacresol — are  both  much  stronger  germicides  than  liquor 
cresolis  compositus  made  from  a  low-boiling  cresol,  which  approximates  ortho- 
cresol. 

"(3)  Liquor  cresolis  compositus  made  from  commercial  cresols  may  be 
expected  to  vary  somewhat  in  germicidal  efficiency,  owing  to  variations  in  the 
boiling  points  of  the  cresols  it  contains.  This  variation,  however,  does  not 
render  it  unreliable  as  a  disinfectant,  as  a  solution  of  liquor  cresolis  com- 
positus made  from  the  lowest-boiling  and  least-active  cresol  was  found  to 
possess  stronger  germicidal  properties  than  carbolic  acid. 

"  (4)  The  germicidal  value  of  liquor  cresolis  compositus  made  from  cresol 
which  boils  at  a  temperature  approximating  orthocresol  (187°  to  189°  C.)  is 
nearly  one  and  one-half  times  greater  than  carbolic  acid." 

Solids  and  Semi-Solids 
Ointments.     (III-2-A) 
There  appears  to  be  very  little  of  such  sold  in  the  state  as  only  one 
sample  came  in  for  inspection. 

Powders.      (III-2-B) 
Various  powdered  substances  such  as  slaked  lime,  borax,  kiesel- 
guhr,  calcium  sulfite,  blast  furnace  slag  and  others  are  said  to  be 
used  for  the  absorption  of  crude  carbolic  acid.     Their  use,  however, 
is  limited  and  their  efficiency  not  very  great. 

Soaps.    (III-2-C) 
Soaps  containing  phenols  have  quite  an  extended  use  on  dogs  and 
other  pet  animals  for  the  eradication  of  fleas  and  lice. 

7  U.  S.  Dept.  Agr.,  Bur.  Animal  Ind.,  Bull.  100,  1907. 


344  UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 

USES   OF   THE    EMULSIFIABLE   PHENOLIC    LIQUIDS 
As  a  Fungicide 

According  to  amendment  Number  Two  to  the  rules  and  regulations 
for  carrying  out  the  provisions  of  the  United  States  Insecticide  Act 
of  1910,  the  Insecticide  Board  of  the  United  States  Department  of 
Agriculture  has  made  the  following  definition  of  the  term  ' '  fungi : '  '8 
' '  The  term  '  fungi '  as  used  in  the  act  and  these  regulations,  is  under- 
stood to  mean  all  nonchlorophyll-bearing  plants  of  a  lower  order  than 
mosses  and  liverworts  (i.e.,  nonchlorophyll-bearing  thallophytes). 
comprising  rusts,  smuts,  molds,  yeasts,  bacteria,  etc." 

This  interpretation  of  the  meaning  of  the  word  fungi  would  neces- 
sitate making  the  statement  that  the  use  of  the  so-called  carbolic  dips 
and  disinfectants  as  fungicides  is  very  extensive.  Preparations  of  this 
sort  with  high  and  dependable  phenolic  content  are  very  valuable 
bactericides.  The  phenols  being  of  the  cresol  type,  they  are  even 
better  than  phenol  for  the  destruction  of  bacteria  and  have  the  ad- 
vantage over  the  latter  in  being  miscible  with  water  in  any  desired 
strength  and  of  possessing  marked  detergent  properties.  The  veter- 
inarian and  stockman  find  use  for  them  as  an  antiseptic  wash  for 
wounds  and  ulcers  and  the  disinfection  of  surgical  instruments.  An 
important  manufacturer  has  advocated  the  use  of  a  dip  in  a  bath  for 
swine  claiming  thereby  to  prevent  the  introduction  of  hog  cholera, 
this  latter  claim  being  to  some  extent  held  by  veterinarians. 

As  an  Insecticide 
It  is  claimed  by  some  that  a  properly  made  dip  of  this  kind  is  more 
efficient  for  the  destruction  of  the  mite  causing  scabies  in  sheep  than 
either  tobacco  or  lime-sulfur  dips.  This  view  is  not  held  by  the  of- 
ficials in  California  who  have  charge  of  the  eradication  of  sheep  scab. 
It  is  thought  that  their  views  are  perhaps  to  a  certain  extent  the  con- 
sequence of  experience  with  improperly  made  dips. 

A  number  of  widely  used  remedies  for  the  destruction  of  the  mange 
mite  are  essentially  of  the  type  of  compounds  under  discussion. 

Essig9  considers  that  ' '  the  most  satisfactory  of  all  the  sprays  used 
in  combating  the  citrus  mealy  bug  is  the  carbolic  acid  emulsion."  The 
preparation  recommended  is  made  as  follows: 

Crude  Carbolic  Acid  5  gals. 

Whale  Oil  Soap  40  lbs. 

Water    (Hot)    40  gals. 

s  Amendment  3  to  Circ.  34,  Office  of  the  Sec,  U.  S.  Dept.  Agr. 
»  Pomona  College  Journal  of  Entomology,  Vol.  II,  No.  3,  p.  252,  1910.     Mo. 
Bull.,  Calif.  State  Com.  of  Hort.,  Vol.  Ill,  No.  2,  p.  82,  1914. 


PHENOLIC    INSECTICIDES    AND    FUNGICIDES  345 

''The  40  gallons  of  water  are  first  poured  into  the  cooking  kettle  and 
allowed  to  boil.  While  the  water  is  getting  hot,  the  whale  soap  is  cut  into 
fine  pieces  so  as  to  make  it  dissolve  easily,  and  added  to  the  water.  When  the 
soap  is  all  dissolved  in  the  hot  water,  the  carbolic  acid  is  added,  and  all  is 
allowed  to  boil  for  a  short  time  to  insure  thorough  mixing." 

The  above  mixture  could  have  been  called  "sheep  dip"  if  intended 
for  use  in  dipping  sheep,  or  if  the  article  has  been  made  up  for  sale  in 
concentrated  form,  any  of  the  names  listed  in  table  5  might  be  applied 
to  it.  If  the  soap  were  composed  partly  of  rosin,  any  name  in  table  6 
would  be  equally  applicable. 

Various  preparations  of  this  class  have  been  successfully  used  for 
the  eradication  of  insects  affecting  the  date  palm,  more  especially  for 
the  dipping  of  the  young  imported  shoots. 

Horticulturists  and  entomologists  have  occasionally  recommended 
similar  preparations  for  the  control  of  insects  and  fungi  infesting 
vegetation,  but  their  use  in  this  connection  has  been  comparatively 
limited,  as  the  results  accomplished  have  not  been  uniform.  At  present 
the  use  of  these  is  not  recommended  to  any  great  extent,  except  as 
noted  above  for  the  control  of  the  citrus  mealy  bug  and  insects  affect- 
ing the  date  palm. 

In  talking  with  men  who  have  experimented  with  the  use  of 
emulsifiable  phenolic  insecticides  there  is  usually  the  same  comment 
made  that  good  results  are  sometimes  obtained  but  often  the  results 
are  valueless.  Frequently  oil-tar  residues10  are  sold  under  the  name 
of  crude  carbolic  acid.  Specimens  have  been  examined  by  this  lab- 
oratory which  appear  to  be  saturated  solutions  of  naphthalene  to 
which  has  been  sparingly  added  enough  cresol  bearing  creosote  to  give 
it  a  "flavor"  of  phenols.  Furthermore,  the  crude  carbolic  acids  are 
too  often  adulterated  with  petroleum  distillates.  It  is  therefore  not 
to  be  wondered  at  that  the  material  at  times  refuses  to  emulsify  or  if 
it  does  emulsify,  the  results  are  erratic.  It  seems  that  this  condition 
of  affairs  may  be  easily  accounted  for  by  the  study  of  results  of 
analyses  reported  in  this  bulletin.  The  favorable  results  reported  by 
Essig  may  be  accounted  for  by  the  possibility  that  he  was  unusually 
fortunate  in  securing  good  specimens  of  crude  carbolic  acid. 

If  products  of  this  sort  and  the  crude  materials  from  which  they 
are  made  could  be  standardized  and  materials  of  reasonable  depend- 
ability could  be  purchased  from  season  to  season,  it  is  thought  that 
the  coal-tar  products  in  general  might  be  extended  to  a  far  wider 
field  of  usefulness  than  at  present. 


io  See  Oil-tar  Creosote,  p.  338. 


346 


UNIVERSITY    OP    CALIFORNIA EXPERIMENT    STATION 


Part  II 

CLASSIFICATION  AND  TABULATION  OF  THE  RESULTS 

OF  ANALYSIS  OF  SAMPLES  TAKEN  IN  FISCAL 

YEAR  1911-1912-1913,  AND  COMMENTS 


No.  Obtained  from 

1037      Brunswig  Drug  Co., 

Los   Angeles. 
1040      Brunswig  Drug   Co., 

Los  Angeles. 
1070      Western  Wholesale  Drug  Co., 

Los  Angeles. 
1423      Kirk,  Geary  &  Co., 

Sacramento. 


TABLE  I 

Description  of  Samples 
(Taken  in  fiscal  year  1911-1912) 
Manufacturer 


Unknown 


Unknown 


Unknown 


The    Hoffman  LaRoche    Chemi- 
cal Works,   New  York. 


Brand 
Liquefied   Carbolic   Acid. 

Carbolic   Acid,    White    Crys- 
tals. 
Carbolic    Acid. 

Roche-Cryst,      40/42°,      U. 
S.  P. 


TABLE  11 

Description  of  Samples 
(Taken  in  fiscal  year  1911-1912) 


No. 

Obtained  from 

Manufacturer 

Brand 

523 

California    Drug   &    Chem 
Co.,   Los  Angeles. 

ical 

Unknown 

Braucco    Cresol. 

0 

Taken 

in  fiscal  year  1912-1913) 

1608 

Hatzfeld   &    Parsons, 
Santa  Ana. 

Unknown 

Cresol. 

2509 

California    Drug    &    Chem 
Co.,    Los  Angeles. 

ical 

Unknown 

Acid    Cresylic. 

2571 

Western  Wholesale  Drug 
Los  Angeles. 

Co., 

Unknown 

Cresol.     (U.   S.  P.) 

2585 

Brunswig  Drug  Co., 
Los  Angeles. 

Unknown 

Cresol.     U.    S.    P.    so-cal 
coal-tar     Creosote. 

3052 

Crystal  Drug  Store, 
Oroville. 

Unknown 

Cresol. 

3353 

Coffin-Redington   Co., 
San  Francisco. 

Unknown 

Cresol. 

3366 

Langley  &  Michaels, 
San   Francisco. 

Unknown 

Cresol.       (Cresylic    Acid) 

PHENOLIC    INSECTICIDES    AND    FUNGICIDES 


IU7 


TABLE  I 
I.  Eefined  Phenols 

1.  Phenol  or  Carbolic  Acid 


Guaranteed 

Absolute 

Phenol 

Found 
Absolute 
Phenol 

Gu; 

arar 

itee 

No. 

Above 

> 
Below 

Remarks 

% 

% 

% 

% 

1037 

91.65 

Liquefied,    Colorless. 

1040 

98.61 

Mostly    white    crystals, 
some  liquid. 

1070 

96.0 
(U.S.  P.) 

98.99 

2.99 

Pink   Crystals. 

1423 

96.0 

99.34 

3.34 

Loose  crystals. 

TABLE  II 
I.  Refined  Phenols 
2.  Cresol  or  Cresylic  Acid 


r 
Phenol 

A 

Cresol 

Total 
Phenols 

Found 

Total 

Phenols 

Guarantee 

A 

So. 

Above         Below 

% 

% 

% 

% 

%                 % 

523 

95-99 

95-99 

98.0 

3.0                

Remarks 


1608 
2509 
2571 
2585 
3052 
3353 
3366 


5.2 


95- 

-99 

95-99 

95- 

-99 

95-99 

100.00 

95, 

,00 

95.00 
95-99 

95-99 

90 

.2 

95.4 

48.48 

96.75 

1 

,75 

93.49 

99.35 

4, 

,35 

48.27 

97.17 

2 

,  17 

98.68 

3 

.28 

Mislabeled1 


51 


Mislabeled1 


1  Samples  No.  1608  and  3052  are  not  cresylic  acids  nor  cresol,  but  are  compounds  similar 
to  "liquor  cresolis  compositus."  Both  are  soluble  in  water,  faintly  alkaline  and  contain  an 
oily  soap. 


348 


UNIVERSITY    OF    CALIFORNIA- -EXPERIMENT    STATION 


TABLE  III 

Description  of  Samples 
(Taken  in  fiscal  year  1911-1912) 


No.  Obtained  from 

521  California    Drug    &    Chemical 

Co.,   Los  Angeles. 

522  California    Drug    &    Chemical 

Co.,   Los  Angeles. 
567     Western  Wholesale  Drug  Co., 

Los  Angeles. 
708      Bean    Spray  Pump   Co., 

San  Jose. 
1042      Brunswig  Drug  Co., 

Los  Angeles. 
1056      Sun  Drug  Co., 

Los  Angeles. 
1130      Coffin    Redington    Co., 

San  Francisco. 
1232      Braun-Knecht-Heimann   Co., 

San  Francisco. 
1424      Kirk,  Geary  &  Co., 

Sacramento. 

2502  California    Drug    &    Chemical 

Co.,   Los  Angeles. 

2503  California    Drug    &    Chemical 

Co.,   Los  Angeles. 
2545      Aggeler  &  Musser  Seed  Co., 

Los  Angeles. 
2550      Western  Wholesale  Drug  Co., 

Los  Angeles. 
2566      Western  Wholesale  Drug  Co., 

Los  Angeles. 
3035      C.   C.  Rubel, 

Marysville. 
3037      Stuck's    Pharmacy, 

Marysville. 
3062      J.  E.   Sangster, 

Oroville. 
3082      Orr's  Drug  Store, 

Willows. 
3102      The  Willows  Pharmacy, 

Willows. 
3111      Oscar  Robinson, 

Colusa. 
3123     John  F.  Fouch, 

Williams. 
3185      Ed.   F.  Johnson, 

Gilroy. 
3209      The  Owl  Drug  Co., 

San  Francisco. 
3229      Coffin  Redington  Co., 

San  Francisco. 
3345      Braun-Knecht-Heimann     Co.. 

San  Francisco. 
3365      Langley  &  Michaels  Co., 

San  Francisco. 
Brunswig  Drug  Co., 

Los  Angeles. 


Manufacturer 
Blagden    &    Waugh 

Blagden  &  Waugh 

Blagden   &  Waugh 

W.    P.    Fuller   &    Co.    (Agent). 
San    Francisco 
Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Unknown 

Carbon    Paint    &    Creosote    Co 


Brand 

7?c-10%    Crude   Carbolic 
Acid. 

15%-25%    Crude    Carbolic 
Acid. 

"Western"   Crude   Carbolic- 
Acid. 

Crude  Carbolic. 

Crude  Carbolic  Acid. 
Carbolic  Acid,  Crude. 
Carbolic  Acid,  Crude. 
Crude  Carbolic  Acid. 
Crude  Carbolic  Acid. 
Crude  Carbolic  Acid. 
Crude  Carbolic  Acid. 
Crude  Carbolic  Acid. 
Creosote  Oil. 
Acid  Carbolic,  Crude. 
Acid  Carbolic,  Crude. 
Acid  Carbolic.  Crude. 
Acid  Carbolic,  Crude. 
Acid  Carbolic,  Crude. 
Acid  Carbolic,  Crude. 
Acid  Carbolic,  Crude. 
Acid  Carbolic,  Crude. 
Acid  Carbolic,  Crude. 
Acid  Carbolic,  Crude. 
Acid  Carbolic,  Crude. 
Acid  Carbolic,  Crude. 
Acid  Carbolic,  Crude. 
Acid  Carbolic,  Crude. 


PHENOLIC    INSECTICIDES    AND    FUNGICIDES 


!U9 


II. 


Crude  Phenols  TABLE  III 

1.  Coal-tar  Creosote  1  Commercial  terms  applied  to  mixed  residues 

2.  Creosote  Oil.  I        from    tar    refineries    containing   variable 

3.  Crude  Carbolic  Acid  amounts  of  phenols. 


Guaranteed 

A 

Found 

Total 

Phenols 

% 

Guarantee 

Phenol 

Cresol 

7c 

Total 
Phenols 

No. 

r    '                           "\ 
Above         Below 

%                 % 

Remarks 

.V.!  1 

7-10 

7-10 

15-25 

7-10 

11.0 
22.4 
13.0 
12.7 
11.6 

4.0                

7.4                

6.0                 

522 

567 

708 

1042 

1056 

19.6 
17.5 

1130 

1232 

12.4 

1424 

38.4 

2502 

7-10 
15-25 

11.0 

27.6 
11.2 

4.00              

12.6                

2503 

2545 

2550 

15-18 

15-18 

17.4 

2.4 

2566 

7-10 

7-10 

9.2 

2.2                

3035 

15- 

-20 

20-25 

35-45 

5.2 

29.8 

3037 

15- 

-20 

20-25 

35-45 

17.0 

18.0 

3062 

15- 

-20 

20-25 

35-45 

18.2 

16.8 

3082 

15- 

-20 

20-25 

35-45 

17.6 

17.4 

3102 

15- 

-20 

20-25 

35-45 

20.4 

14.6 

3111 

15- 

-20 

20-25 

35-45 

18.0 

17.0 

3123 

15- 

-20 

20-25 

35-45 

18.0 

17.0 

3185 

15- 

-20 

20-25 

35-45 

18.0 

17.0 

3209 

25- 

-30 

25-30 

17.8 

7.2 

3229 

21 

.0 

25.0 

46.0 

18.2 

27.8 

3345 

7-10 

7-10 

12.2 

5.2                

3365 

17 

.6 

8.25 

25.85 

11.6 

14.25 

15 

-20 

10-12 

25-32 

4.9 

20.1 

Unofficial 

350 


UNIVERSITY    OF    CALIFORNIA — EXPERIMENT    STATION 


TABLE  IV 

Description  of  Samples 
(Taken  in  fiscal  year  1911-1912) 


No. 

Obtained  from 

Manufacturer 

Germo   Manufacturing  Co., 

Germo   Manufacturing  Co., 

Los  Angeles. 

Los  Angeles. 

21 

Winters  Pharmacy, 

Spratt's    Patent    (America), 

Winters. 

ltd. 

53 

Red  Raven   Drug  Co.,    Inc., 

H.  Clay  Glover,  D.  V.   S., 

San  Francisco. 

New  York. 

84 

Rossi  Drug  Co., 

Dr.    G.   W.   Clayton, 

San   Francisco. 

Chicago. 

155 

White  Cross  Drug  Co., 

Petaluma  Incubator  Co., 

Santa  Ana. 

Petaluma. 

163 

Star  Drug  Co., 

Geo.    H.    Lee, 

Santa  Monica. 

Omaha,    Nebr. 

212 

Hardman's  Drug  Store, 

F.   C.    Sturtevant, 

Riverside. 

Hartford,   Conn. 

237 

Aitken's   Pharmacy, 

The  G.   E.   Conkey  Co., 

Calexico. 

Cleveland,    Ohio. 

238 

Aitken's    Pharmacy 

Geo.    H.    Lee, 

Calexico. 

Omaha,    Nebr. 

253 

City  Drug  Co., 

Sacramento    Chemical   Co., 

Lemoore. 

Sacramento. 

263 

Wright  Bros., 

Gold  Coin   Chemical  Works, 

Selma. 

St.    Paul,    Minn. 

274 

Fabian-Grunauer    Co., 

Carpenter-Morten   Co., 

Tracy, 

Boston,   Mass. 

275 

Fabian-Grunauer   Co., 

Manhattan    Food    Co., 

Tracy. 

Oakland. 

446 

Osgood's   Drug    Store, 
Oakland. 

F.    S.    Burch    Co. 

714 

The    Manufacturer, 

West   Disinfecting   Co., 

San  Francisco. 

San  Francisco. 

901 

The    Manufacturer. 

Oregon   Wood   Distilling   Co. 
Linnton,    Oregon. 

1002 

The    Manufacturer. 

Geo.  H.  Lee, 
Omaha,   Nebr. 

1004 

The  Manufacturer. 

Henry  Albers   Co., 
Los    Angeles. 

1059 

The    Manufacturer. 

West  Coast  Mill, 

(Thompkins    &    Co.) 

Los  Angeles. 

1063 

The    Manufacturer. 

West   Coast  Mill, 

(Thompkins    &    Co.) 

Los  Angeles. 

1503 

The  Manufacturer. 

Petaluma  Incubator  Co., 
Petaluma. 

1515 

The  Manufacturer, 

Geo.  H.   Lee   Co., 

Los  Angeles. 

Omaha,    Nebr. 

2104 

The  Manufacturer. 

Kirk,   Geary  &   Co., 
Sacramento. 

2246 

Geo.  H.  Croley  Co., 

F.    C.    Sturtevant    Co., 

San  Francisco. 

Hartford,    Conn. 

Brand 


Germo. 


Spratt's  Eczema  and  Mange 

Cure. 
Glover's  Imperial  Mange 

Remedy. 
Clayton's  Mange  Remedy. 

Creosozone. 

Lee's  Lice  Killer. 

Creo-Carbo. 

Conkey' s  Fly  Knocker. 

Flyo-Curo. 

No-Fly. 

Gold  Coin  Lice  Killer. 

Cow-Ease. 

Fly  Keep  Off. 

Sanford's  Lice  Killer. 

Kill-Bug. 

Orwood  Lice  Killer. 

Lee's  Lice  Killer 

Alber's  Liquid  Lice  Killer. 

W.   C.   Lice  Killer. 

Flyfoe. 

Creosozone  Liquid  Lice 

Killer. 
Lee's  Lice  Killer. 

Fornolice. 

The  Sturtevant  Lice  Paint. 


PHENOLIC    INSECTICIDES    AND    FUNGICIDES 


nr>i 


TABLE  IV 

III.  Compounded  and  Proprietary  Remedies 
1.  Liquids 

A.  Insoluble  in  water 
(a)   Non-emulsifiable 


Guaranteed 

A 

Found 

Total 

Phenols 

Guarantee 

K 

Phenol 

Cresol 

Total 

Phenols 

No. 

Above         Below 

% 

% 

% 

% 

%                 % 

3.8 
0.6 
7.6 
1.0 
0.4 

21 

53 

84 

155 

163 

7.2 
22.8 

o  jo 

237 

2.2 

238 

2.4 

253 

0.4 

263 

6.6 

274 

10.8 

275 

1.4 

446 

0.8 

714 

10.0 

10. 

0 

13.1 

3.1                

901 

4.0 

1002 

6. 

0 

8.8 

2.8                

1004 

12.0 

3.13 

15. 

13 

19.4 

4.27             

1059 

1.4 

1063 

1.4 

1503 

(1) 

9.1 

1515 

6 

.0 

1.26 

4.74 

2104 

7- 

-10 

18.0 

11.0                

2246 

6 

.0 

14.82 

8.82             

(1)  Creosotum  81.2%. 

Remarks 


352 


UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 


TABLE  IV— (Continued) 

Description  of  Samples 

(Taken  in  fiscal  year  1911-1912) 


No.  Obtained  from 

2547      Aggeler  &  Musser  Seed  Go., 

Los  Angeles. 
2603      The  Manufacturer. 

2611      Thompkins  &  Co., 

Los  Angeles. 
2615      Thompkins  &  Co., 

Los  Angeles. 
2620      Thompkins  &  Co., 

Los  Angeles. 


Manufacturer 
Unknown 

Henry  Albers  Co., 

Los  Angeles. 
West    Coast    Mill    (Thompkins 

&  Co.),  Los  Angeles. 
West    Coast    Mill    (Thompkins 

&  Co.),   Los  Angeles. 
West    Coast    Mill    (Thompkins 

&  Co.),  Los  Angeles. 


Brand 

A  &  M  Lice  Killer. 

Alber's  Liquid  Lice  Killer. 

Scalefoe. 

West  Coast  Lice  Killer. 

Flyfoe. 


No.  Obtained  from 

215      Hardman's   Drug   Store, 

Riverside. 
717     Catfon  Bell  &  Co., 

San  Francisco. 
1011      The  Manufacturer. 


23  75      The   Manufacturer. 

2594      Brunswig  Drug   Co. 
Los,   Angeles. 


TABLE  V 
Description  of  Samples 

(Taken  in  fiscal  year  1911-1912) 

Manufacturer 
Dr.  David  Roberts  Veterinary 

Co.,    Waukesha,   Wisconsin. 
Morris  Little  &   Son, 

Doncaster,    England. 
McStay    Supply    Company, 

Los  Angeles. 

(Taken  in  fiscal  year  1912-1913) 
Standard  Chemical  Co., 

Oakland. 
Unknown 


Brand 
Dr.  David  Roberts'  Germ 

Killer. 
Little's    Improved    Fluid 

Dip. 
Stayco  Sheep  Dip. 


Ideal  Stock  Dip. 
Cre-aseptol. 


TABLE  VI 

Description  of  Samples 
(Taken  in  fiscal  year  1911-1912) 


No. 

Obtained  from 

Manufacturer 

Brand 

1 

The   Manufacturer. 

George   H.   Aspinwall, 
Jersey  City,  N.  J. 

Phenocide. 

35 

California   Pharmacy, 

Dr.  G.  W.  Clayton, 

Ceoline  Dog  W 

San  Francisco. 

Chicago,   111. 

PHENOLIC    INSECTICIDES    AND    FUNGICIDES 


353 


TABLE  YV— (Continued) 
111.  Compounded  and  Proprietary  Remedies 
1.  Liquids 

A.  Insoluble  in  water 
(a)   Non-emulsifiable 
Guaranteed 


No. 

Phenol 

% 

Cresol 

% 

Total 
Phenols 

% 

Found 

Total 

Phenols 

% 

2547 

12.00 

3.13 

15.13 

1.70 

2603 

12.00 

3.13 

15.13 

19.08 

2611 

18.5 

18.5 

2.12 

2615 

1.02 

2620 

3.13 

3.13 

1.86 

Guarantee 

, A > 

Above         Below 

%                 % 

13.43 

3.95 

16.38 
1.27 

Remarks 


TABLE  V 
III.  Compounded  and  Proprietary  Eemedies 
1.  Liquids 

A.  Insoluble  in  water 
(b)   Emulsiftable 

(1)   With  Fatty  Soap  Emulsifier 
Guaranteed 


Phenol 

% 

Cresol 

% 

Total 
Phenols 

% 

Found 

Total 

Phenols 

% 

Guarantee 

A 

No. 

Above 

% 

Below 

% 

Remarks 

215 

62.5 

717 

17.0 

16.6 

0.4 

1011 

2375 
2594 

70.0 
36.0 

(1) 

70.0 
36.0 

4.1 

71.86 
35.68 

1.86 

0.32 

(1)  Crude  Carbolic  Acid — 25.0% 


No. 
1 
35 


TABLE  VI 
III.  Compounded  and  Proprietary  Eemedies 
1.  Liquids 

A.  Insoluble  in  water 
(b)   Emulsiftable 

(2)    With  Bosin  Soap  Emulsifier 


Guaranteed 

A 


Phenol        Cresol 

%  % 


Total 

Phenols 

% 


Found 
Total 

Phenols 
% 
9.4 

14.0 


Guarantee 


Above         Below 

%  % 


Remarks 


354 


UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 


TABLE  VI—  (Continued) 
Description  of  Samples 


(Taken  in  fiscal  year  1911-1912) 


No.  Obtained  from 

59      Bass-Hueter  Paint  Co., 

San  Francisco. 
66      Edwin   Val   Schmidt, 

San  Francisco. 
86      Rossi  Drug  Co., 

San  Francisco. 
89      Rossi  Drug  Co., 

San  Francisco. 
121      Lacey   &   Hartsough, 

San   Diego. 
182      Barritt  Drug  Co., 

Long  Beach. 
186      Oakford  Drug  Co., 

Long  Beach. 
194     Jacob  Jesson, 

Ontario. 
197     Collins   Pharmacy, 

Uplands. 
200     Alhambra   Drug    Store, 

Alhambra. 
259      Reliable   Pharmacy, 

Kingsburg. 
261      Reliable   Pharmacy, 

Kingsburg. 
273      Fabian-Grunauer   Co., 

Tracy. 
422      Clayton  Square  Drug  Store, 

East   Oakland. 
435      Bowman  Drug  Co., 

Oakland. 
450      Osgoods  Drug   Store, 

Oakland. 
456      Bowman   Drug  Co., 

Oakland. 
493      Trumball   Seed   Co., 

San  Francisco. 

496  Trumball   Seed  Co., 

San  Francisco. 

497  Trumball   Seed  Co., 

San  Francisco. 
546      California  Drug  &  Chemical 
Co.,   Los  Angeles. 

712  West   Disinfecting   Co., 

San  Francisco. 

713  West   Disinfecting   Co., 

San  Francisco. 

718  Catton,   Bell  &  Co., 

San  Francisco. 

719  Catton,   Bell  &   Co., 

San  Francisco. 


Manufacturer 
National    Chemical    Co., 

San  Francisco. 
The   Sulpho-Napthol  Co., 

Boston,    Mass. 
Dr.  A.  C.   Daniels,   Inc., 

Boston,   Mass. 
Johnson  &  Johnson, 

New  Brunswick,   N.   J. 
Wm.    Pearson    (Merck    &    Co., 

Agents),    New   York. 
West   Disinfecting   Co., 

New  York. 
Park,  Davis  &  Co., 

Detroit,  Mich. 
Zenner  Disinfectant  Co., 

Detroit,  Mich. 
Dr.  Hess  &  Clark, 

Ashland,    Ohio. 
Sharp  &  Dohme, 

Baltimore,   Md. 
Security   Remedy   Co., 

Minneapolis,  Minn. 
Stockmen's    Supply   Co.. 

Fresno. 
Scott  &  Gilbert  Co., 

San  Francisco. 
Park,   Davis  &  Co., 

Detroit,  Mich. 
Bowman  &  Co., 

Oakland. 
Merton    &    Co.,    Sole    Agents, 

San  Francisco. 
Morris,    Little   &   Son, 

Doncaster,    England. 
Coulson  Poultry  &  Stock  Food 

Co.,   Petaluma. 
The  G.  E.   Conkey  Co., 

Cleveland,   Ohio. 
The  G.  E.  Conkey  Co., 

Cleveland,   Ohio. 
California  Drug  and  Chemical 

Co.,   Los  Angeles. 
West  Disinfecting  Co. 

West  Disinfecting  Co. 

Morris,    Little   &    Son. 

Doncaster,    England. 
Morris,   Little  &  Son., 

Doncaster,    England. 


Brand 
Creofect. 

Cabot's    Sulpho-Napthol. 

Carbo-Negus. 

Red  Cross   Sanitary   Fluid. 

Creolin-Pearson. 

"C  N"   Disinfectant. 

Kreso. 

Zenoleum. 

Dr.  Hess'  Dip  and  Disin- 
fectant. 
Sanax  Disinfecting  Fluid. 

Security  Carbolized  Disin- 
fectant. 
Stockmen's    Antiseptic   Dip. 

S  &  G  Poultry  Lice  Killer. 

Kreso  Dip  No.  1. 

Creophene. 

Merton's   Phenolene. 

Little's   Soluble  Phenyl.  . 

Cresolene. 

Conkey's  Lice  Liquid. 

Noxicide. 

Cresylol. 

Chloro-naptholeum. 

Chloro-naptholeum   Dip. 

Little's   Special  Fluid  Dip. 

Little's  Soluble  Phenyle. 


PHENOLIC    INSECTICIDES    AND    FUNGICIDES 


355 


TABLE  VI—  (Continued) 
III.  Compounded  and  Proprietary  Remedies 
1.  Liquids 

A.  Insoluble  in  water 
(b)   Emulsifiable 

(2)    With  Eosin  Soap  Emulsifier 


Guaranteed 

A 

Found 

Total 

Phenols 

% 
10.8 

14.2 

14.4 

23.2 

17.4 

3.8 
25.2 
14.4 
14.2 
15.8 
16.2 
12.0 
16.2 
19.4 
12.4 
12.2 
12.4 
11.8 

8.2 
12.6 
17.6 
20.49 
14.6 
10.87 
12.6 

Guarantee 

A 

Phenol        Cr 

% 

12 

esol 

% 

T« 
Phe 

18- 
26 
10 
12 
20 

jtal 
nols 

% 

No. 
59 

Above         Below 

0.4 

5.61 

4.0               

1.13 

7.4 

Remarks 

66 

86 

89 

121 

182 

186 

194 

197 

200 

259 

261 

273 

422 

435 

450 

456 

493 

496 

497 

546 

-20 

.1 

.6 

.0 

.0 

712 

713 

718 
719 

.00 

:J56 


UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 


TABLE  VI—  {Continued) 
Description  of  Samples 


(Taken  in  fiscal  year  1911-1912) 


No. 

Obtained  from 

722 

Sulpho-Napthol  Co., 

Los   Angeles.     (By  mail). 

1045 

Brunswig  Drug   Co., 

Los  Angeles. 

1061 

Thcmpkins   &   Co., 

Los  Angeles. 

1068 

The  Manufacturer. 

1074 

Western  Wholesale  Drug  Co 

Los  Angeles. 

1114 

Langley  &  Michaels, 

San  Francisco. 

1132 

The  Manufacturer. 

1137 

The  Manufacturer. 

1138 

The  Manufacturer. 

1145 

The  Manufacturer. 

1236 

Scott  &  Gilbert, 

San  Francisco. 

1237 

Scott  &  Gilbert, 

San  Francisco. 

1239 

Scott  &  Gilbert, 

San  Francisco. 

1253 

The  Manufacturer. 

1254 

The  Manufacturer. 

1255 

The  Manufacturer. 

1256 

The  Manufacturer. 

1257 

The  Manufacturer. 

1271 

The  Manufacturer. 

1520 

The  Manufacturer. 

1629 

White  Cross  Drug  Co., 

Santa  Ana. 

1666 

Halsell  Drug  Co., 

Huntington  Beach. 

1720 

Mullinix's  Store, 

Anaheim. 

2030 

N.   L.   A.   Cody, 

Merced. 

2043 

W.  W.  W.  Hunter, 

Madera. 

Manufacturer 
Unknown 


Unknown 


West  Coast  Mill  (Thompkins 
&  Co.),  Los  Angeles. 

Germo  Manufacturing  Co.  of 
California,    Los   Angeles. 

Unknown 

National    Aniline    &    Chemical 

Co. 
Coffin-Redington    Co., 

San  Francisco. 
The  Owl  Drug  Co., 

San  Francisco. 
The  Owl  Drug  Co., 

San  Francisco. 
The  Owl  Drug  Co., 

San  Fi'ancisco. 
California   Compounding  Co., 

San  Jose. 
California    Compounding   Co., 

San  Jose. 
California    Compounding   Co., 

San  Jose. 
W.  P.  Fuller  &  Co., 

San  Francisco. 
W.  P.  Fuller  &  Co., 

San  Francisco. 
W.  P.  Fuller  &  Co., 

San  Francisco. 
W.  P.  Fuller  &  Co., 

San  Francisco. 
W.  P.  Fuller  &  Co., 

San  Francisco. 
Shumate's   Pharmacy,    Inc., 

San  Francisco. 
Geo.  H.  Lee  Co., 

Omaha,  Nebr. 
Western   Wholesale   Drug   Co., 

Los  Angeles. 
Park,  Davis  &  Co., 

Detroit,  Mich. 
Park,  Davis  &  Co., 

Detroit,  Mich. 
Unknown 

Morris,  Little  &   Son, 
Doncaster,    England. 


Brand 
Carbo-Napthol. 

Sheep  Dip. 

Germioe. 

Germo-Carbolene. 

Imperial  Sheep  Dip. 

Cresolite  Sheep  Dip. 

Creofenol  Dip. 

The  Owl  Drug  Co.  Sheep 

Dip. 
The  Owl's  Soluble  Phenyl. 

Todco  Mange  Remedy. 

S  &  G  Sheep  Dip. 

S  &  G  Lice  Killer. 

S  &  G  Chicken  Dip  &  Lice 

Killer. 
Fuller's   Carbolic  Tree 

Spray. 
Fuller's  Carbolic  Rose  and 

Vine  Spray. 
Fuller's   Carbolic   Hop 

Spray. 
Fuller's  Carbolic   Sheep  Dip 

and  Cattle  Wash. 
Fuller's   Carbolic  Poultry 

Spray. 
Shumate's   Phenyle. 

Lee's   Sheep  Dip. 

Sheep  Dip. 

Sheep  Dip. 

Sheep  Dip. 

Sheep  Dip. 

Little's  Sheep  Dip. 


PHENOLIC   INSECTICIDES    AND    FUNGICIDES 


INS- 


TABLE VI—  (Continued) 
III.  Compounded  and  Proprietary  Remedies 
1.  Liquids 

A.  Insoluble  in  water 
(b)   Emulsifiable 

(2)    With  Rosin  Soap  Emulsifter 


Guaranteed 

A 

Found 

Total 

Phenols 

% 

Guarantee 

A 

Total 
Phenols 

% 

No.                 Phenol        Cresol 

%                    % 

Above         Below 

%                 % 

Remarks 

722 

13.6 

Unofficial 

1045                   

1061 

8.0 
16.0 

1068                   

7.4 

1074                   

22.0 

20.4 

1.6 

1114                   

15.2 

1132                   

20.0 

1137                   

14.6 

1138                   

14.2 

1145                   

15.8 

1236                   15.0 

15.0 

17.0 

2.0 

1237                  15.0 

15,0 

18.8 

3.8                

1239                                      15.0 

15.0 

19.0 

4.U                

1253                  

9.1 

9.2 

0.1^               

1254                  

9.1 

9.4 

0.3                

1255                  .             

9.1 

9.4 

0.3 

1256                  

9.1 

9.0 

0.1 

1257                  

9.1 

9.0 

0.1 

1271                  

27. 01 

26.0 

1.0 

> 

1520                  

5.7 

1629 

22.0 

17.4 

4.6 

1666                  

18.0 

19.4 

1.4                

1720                  

16-22 

16.4 

0.4                

2030                  16-17 

16-17 

16.16 

0.16             

2043                  

13.28 

iPhenyle,  27%. 

358 


UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 


TABLE  VI—  (Continued) 
Description  of  Samples 


(Taken  in  fiscal  year  1911-1912) 


No. 

Obtained  from 

Manufacturer 

2062 

Toda  Bros., 

Security   Remedy  Co., 

Farmington. 

Minneapolis,    Minn. 

2077 

Hotel  Drug  Co., 
Stockton. 

Unknown 

2082 

Royce  &   Youngman, 

Royce  &  Youngman, 

Sacramento. 

Sacramento. 

2125 

P.   Flatow  &   Son, 

Sharp  &  Dohme, 

Alameda. 

Baltimore,    Md. 

2137 

Kennet   Drug   Store, 

Morris,  Little  &   Son, 

Kennet. 

Doncaster,    England. 

2163 

The  Manufacturer. 

Merton   &   Co., 
San   Francisco. 

2165 

The  Manufacturer, 

American    Druggists'     Syndi- 

San  Francisco. 

cate,    New   York. 

2176 

The  Manufacturer. 

W.   P.  Fuller  &  Co., 
San   Francisco. 

2177 

The  Manufacturer. 

\V.    1'.   Fuller  &  Co., 
San  Francisco. 

2178 

The  Manufacturer. 

\Y.    P.  Fuller  &  Co., 
San  Francisco. 

2179 

The  Manufacturer. 

W.   P.  Fuller  &  Co., 
San  Francisco. 

2180 

The  Manufacturer. 

W.   P.  Fuller  &  Co., 
San  Francisco. 

2196 

The  Manufacturer, 

The  Owl  Drug  Co., 

San  Francisco. 

San   Francisco. 

2248 

Catton,   Bell  &   Co., 

Morris,   Little  &   Son, 

San  Francisco. 

Doncaster,    England. 

2250 

The  Manufacturer. 

Robinson    Chemical    Works, 
San   Francisco. 

2508 

The  Manufacturer. 

California    Drug    &    Chemical 
Co.,   Los  Angeles. 

2556 

Western  Wholesale  Drug  Co., 
Los  Angeles. 

Unknown 

2584 

Brunswig  Drug  Co., 
Los  Angeles. 

Unknown 

2610 

Thompkins   &  Co., 

West    Coast    Mill     (Thompkins 

Los  Angeles. 

&  Co.),  Los  Angeles. 

2624 

The  Manufacturer. 

Purolene   Disinfecting   Co., 
Los  Angeles. 

2622 

The  Manufacturer, 

Germo    Manufacturing    Co.    of 

Los  Angeles. 

California,    Los  Angeles. 

2633 

The  Manufacturer. 

Sun  Drug  Co., 
Los  Angeles. 

2653 

The  Manufacturer. 

Los  Angeles  Chemical  Co., 
Los    Angeles. 

2673 

The  Manufacturer. 

Thomas  Drug  Store, 
Azusa. 

3066 

E.   C.  Whiting, 
Oroville. 

Unknown 

Brand 
Security    Carbolized    Disin- 
fectant. 
Sheep  Dip. 

San-i-tin  or  Sheep  Dip. 

Sheep   Dip. 

Sheep   Dip. 

Merton's  Phenolene. 

A.    D.   S.   Kresano. 

Fuller's  Carbolic  Tree 
Spray. 

Fuller's   Carbolic    Hop 

Spray. 
Fuller's  Carbolic  Rose  and 

Vine   Spray. 
Fuller's  Carbolic  Poultry 

Spray. 
Fuller's  Carbolic   Sheep   Dip 

and  Cattle  Wash. 
Todco  Mange  Remedy. 

Little's  Soluble  Phenyle. 

Palo    Alto    Sheep    Dip    & 

Disinfectant. 
Cresylol. 

Imperial  Sheep  Dip. 

Creol  Dip. 

Germfoe. 

Koltarcre. 

Germo  Carbolene. 

Sun  Mealy  Bug  Spray. 

Emulsion    Disinfectant. 

77   Dip.      Disinfecting 

Fluid. 
Sheep  Dip. 


PHENOLIC    INSECTICIDES    AND    FUNGICIDES 


159 


TABLE  VI—  (Continued) 
III.  Compounded  and  Proprietary  Remedies 
1.  Liquids 

A.  Insoluble  in  water 

(b)   Emulsifiable 

(2)    With  Bosin  Soap  Emulsifier 
Guaranteed 


r 

Phenol 

% 

Cre 
15 

15 
15 

A 

sol 

% 

Total 
Phenols 

% 

22.0 

22.0 

17.0 

15-16 

20.0 

9.1 

9.1 

9.1 

9.1 

9.1 

15-17 

20.0 

15.0 

18.0 

22.0 

15.0 

18-20 

9.0 
18.5 
17.0 

Found 

Total 

Phenols 

% 

5.46 

15.36 

14.75 

16.2 

10.68 

13.04 

6.30 
10.58 
10.8 
11.1 
10.5 
10.8 
14.72 
11.48 
15.74 
17.14 
18.46 
15.62 
14.08 
17.18 
10.8 

6.6 
17.2 
16.86 
21.90 

Guarantee 

A 

No 
2062 

Above         Below 

%                 % 

6.64 

7.25 

0.8 

4.32 

6.96 

1.48              

1.7                

2.0                

1.4                

1.7               

0.28 

8.52 

0.74             

0.86 

3.54 

0.62             

0.82 

2.4 

1.3 

0.14 

Remarks 

2077 

label 

2082 

2125 

2137 
2163 

-16 

2165 

2176 

2177 

2178 

2179 

2180 

2196 
2248 

-17 

2250 

2508 

.0 

2556 

2584 

2610 

2624 

2622 

2633 

2653 

2673 

3066 

360 


UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 


TABLE  VI—  (Continued) 

Description  of  Samples 

(Taken  in  fiscal  year  1911-1912) 


No. 

Obtained  from 

Manufacturer 

3076 

The  Lee  Pharmacy, 
Chico. 

Unknown 

3138 

J.   R.    Shelton, 
Woodland. 

Unknown 

3161 

Corner  Drug  Store, 
Woodland. 

Unknown 

3203 

The   Owl  Drug  Co., 
San  Francisco. 

Unknown 

3217 

The   Owl   Drug  Co., 
San  Francisco. 

Unknown 

3224 

Coffin    Redington    Co., 
San  Francisco. 

Unknown 

3253 

Scott  &  Gilbert  Co., 
San  Francisco. 

Unknown 

3254 

Scott  &  Gilbert  Co., 
San   Francisco. 

Unknown 

3292 

The  Manufacturer. 

Shumate's    Pharmacy 
San  Francisco. 

3376 

Langley  &  Michaels   Co., 
San  Francisco. 

Unknown 

3377 

Langley  &  Michaels  Co., 

Unknown 

Brand 
Sheep  Dip. 

Sheep  Dip. 

Sheep  Dip. 

The  Owl's  Soluble  Phenyl. 

Sheep  Dip. 

Creo   Fenol   Sheep  Dip. 

S  &  G  Sheep  Dip. 

S  &  G  Chicken  Dip. 

Shumate's   Phenyl. 

Cresoleum. 

Cresolite  Sheep  Dip. 


San   Francisco. 


No.  Obtained  from 

70  C.   F.  Fuller, 

San  Francisco. 

71  C.   F.  Fuller, 

San  Francisco. 
88      Rossi  Drug  Co., 
San  Francisco. 
1022      Brunswig  Drug  Co. 
Los   Angeles. 


TABLE  VII 

Description  of  Samples 

(Taken  in  fiscal  year  1911-1912) 

Manufacturer 
Hance  Brothers  &  White, 

Philadelphia,   Penn. 
Entrepot    special    de    produits 

Hygeniques,    Paris. 
Lehn  &  Fink, 

New  York. 
Unknown 


1626     White    Cross    Drug    Co., 

Santa  Ana. 
2094     Kirk,  Geary  &  Co., 

Sacramento. 
3256      Central  Drug  Co., 

San  Francisco. 
3386      Langley  &  Michaels  Co., 

San  Francisco. 


(Taken  in  fiscal  year  1912-1913) 
Unknown 

Kirk,   Geary  &   Co., 

Sacramento. 
H.   K.  Mulford  Co., 

Philadelphia,    Penn. 
Unknown 


Brand 
Phenol   Sodique. 

Veritable    Phenol-Baboeuf. 

Lysol. 

Cre-aseptol. 

Solution  Cresol  Compound. 
Kasol.    Liq.  Cresolis  Comp. 
Cresolis  Compound. 
Liquor  Cresolis   Compositus. 


PHENOETC    INSECTICIDES    AND    FUNGICIDES 


361 


TABLE  VI— {Continued) 
III.  Compounded  and  Proprietary  Remedies 
1.  Liquids 

A.  Insoluble  in  water 
(b)   Emulsifiable 

(2)    With  Rosin  Soap  Emulsifier 
Guaranteed 


Total 


No. 
3076 

Phenol 

% 

Cresol 

% 

Phenols 

% 

3138 

16-17 

16-17 

3161 

22.0 

3203 

15-17 

15-17 

3217 

15-17 

15-17 

3224 

22.0 

3253 

15.0 

15.0 

3254 

15.0 

15.0 

3292 

27. 0l 

3376 

16-17 

16-17 

3377 

'Phenyle"  27%. 

16-17 

16-17 

Found 

Total 

Phenols 

% 

Guarantee 

A 

Above 

% 

Below 

% 

10.04 

15.46 

0.54 

24.40 

2.40 

14.6 

0.4 

13.86 

1.14 

16.76 

5.24 

17.30 

2.30 

18.50 

3.50 

17.3 

9.7 

14.58 

1.42 

14.70 

1.30 

TABLE  VII 
III.  Compounded  and  Proprietary  Remedies 
1.  Liquids 

B.  Soluble  in  water  .. 
Guaranteed 


Phenol 

% 

A 

Cresol 

% 

Total 
Phenols 

% 

Found 

Total 

Phenols 

% 

Guarantee 

A 

No. 

Above         Below 

%                 % 

70 

None 

71 

7.2 

88 

52.6 

1022 

35.2 

1626 

50.0 

50.0 

46.5 

3.5 

2094 

50.0 

50.0 

48.84 

1.16 

3256 

45.0 

45.0 

47.54 

2.54              

3386 

50.0 

50.0 

48.66 

1.34 

Remarks 


Remarks 


362 


UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 


TABLE  VIII 
III.  Compounded  and  Proprietary  Kemedies 
2.  Solids  and  Semi-Solids 
A.  Ointments 

No.   233      Cresylic  Ointment  obtained  from  Dunaway's  Pharmacy,   El  Centre      Manu- 
facturer,   Buchan's    Soap    Corporation,   New  York.     Found  Total  Phenols    13 . 0% 


TABLE  IX 
III.  Compounded  and  Proprietary  Remedies 


Guarantee 


2.  Solids  and  Semi-Solids 

B.  Powders 

Total 

A 

No. 

25 
1448 

Phenol 

% 

Guaranteed 
Cresol         Phenols 

%                 % 

Found 

Cresol 

% 

0.36 

1.05 

Above 

%     . 


Below 

% 


Remarks 


TABLE  X 

Other  Samples  Examined 
Users'  Samples  (submitted  in  fiscal  year  1911-12) 


No. 

Sender 

Material 

823 

L.    P.    Spiers, 

Carbolic  Acid  for  spraying 

San  Jose 

purposes 

826 

Bean  Spray  Pump  Co., 

Crude  Carbolic  Acid 

San  Jose 

827 

Charles  Keane,    State  Veterinarian, 

Little's   Improved    Fluid 

Sacramento. 

Dip 

Found 

Total 

Phenols 

% 
18.4 


17.1 

16.8 


Pine  Tar.     (Sample  taken  in  fiscal  year  1911-12) 
542      Obtained   from    California   Drug    & 
Chemical   Co.,    Tjos   Angeles 


7.2 


PHENOLIC    INSECTICIDES    AND    FUNGICIDES  363 


TABLE  JX 

Description  of  Samples 
(Taken  in  fiscal  year  1911-1912) 

No.                  Obtained  from                                        Manufacturer  Brand 

25      The  Manufacturer.                             Langley   &  Michaels  Co.,  Carbolic  Powder  or  Carbo- 

San   Francisco.  lated  Lime. 

1448      Kirk,   Geary  &   Co.,                           Unknown  Compound  Carbolic  Powder. 
Sacramento. 


COMMENTS  ON  THE  RESULTS  OF  ANALYSIS 
Tables  1  and  2 
Examination  of  the  refined  phenols  showed  them  to  be  of  good 
quality   (with  one  exception)   so  far  as  analyzed  in  the  laboratory, 
even  exceeding  the  guarantee  in  most  cases. 

Table  3 
The  amount  of  total  phenols  found  in  the  samples  of  crude  phenols 
varies  from  4.9  per  cent,  to  38.4  per  cent.  This  state  of  affairs  would 
not  be  so  serious  if  the  correct  per  cent,  of  phenols  were  stated  on  the 
label,  or  even  a  close  approximation,  so  that  the  quantity  used  could 
be  varied  according  to  the  strength.  But  when  there  is  a  variation 
of  nearly  30  per  cent,  from  the  guarantee,  as  was  found  in  one  sample, 
and  a  frequent  variation  of  15  to  18  per  cent.,  a  very  unsatisfactory 
condition  must  be  admitted  to  exist  in  regard  to  the  crude  phenols. 

Table  4 
These  compounds  present  a  very  inviting  field  for  research  to  the 
chemist,   composed  as  they   are   of  so  many  substances   of   difficult 
separation  and  identification.     In  many  of  these  the  oils  and  sub- 
stances other  than  phenols  are  evidently  the  most  active  as  insecticides, 


364  UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 

so  that  the  determination  of  the  phenols  can  not  be  construed  as  a 
comparison  of  their  efficiency.  Inasmuch  as  the  percentage  of  phenols 
was  declared  in  many  of  such  preparations,  this  constituent  was  de- 
termined and  may  serve  as  an  index  of  their  reliability  in  other 
respects,  where  the  composition  is  given.  A  large  number  of  them 
being  by-products  from  the  oil  and  coal-tar  refineries  it  is  to  be  ex- 
pected that  the  composition  would  vary  greatly  in  respect  to  one  of 
the  more  valuable  commercial  products  of  the  refineries:  namely,  the 
phenols.  Of  the  eleven  samples  with  labels  stating  the  percentage  of 
active  constituents,  one  stated  creosotum  as  an  active  constituent 
which  in  itself  is  a  very  uncertain  compound,  six  were  above  guar- 
antee, and  four  below  guarantee.  In  this  group  then,  there  is  decided 
room  for  improvement. 

Table  5 

Of  the  preparations  listed  in  this  table,  one  containing  an  unusu- 
ally high  phenolic  content  was  found  to  be  even  above  the  guarantee ; 
two  were  only  very  slightly  below,  but  well  within  the  5  per  cent, 
limit;  one  is  passable  on  account  of  an  indefinite  guarantee  of  crude 
carbolic  acid ;  and  one  had  no  statement  of  active  ingredients  but  was 
found  to  have  an  unusually  high  phenolic  content. 

These,  then,  are  fairly  satisfactory  in  conforming  to  guarantee, 
although  the  variation  in  total  phenols  is  rather  remarkable,  ranging 
from  4.1  per  cent,  to  71.86  per  cent. 

Table  6 

Thirty-nine  samples  of  this  group  without  guarantee  were1  ex- 
amined. The  percentage  of  total  phenols  varied  from  3.8  per  cent,  to 
25.2  per  cent.  Forty-nine  samples  were  examined  which  bore  labels 
stating  the  percentage  of  active  constituents.  Of  these  latter,  twenty 
were  up  to  standard  in  phenolic  content  and  twenty-nine  below.  A 
5  per  cent,  deficiency  was  allowed  in  the  law  before  it  was  amended, 
without  being  considered  a  case  of  misbranding.  This  provision  takes 
out  eleven  of  the  twenty-nine  from  those  in  the  below-grade  class  and 
places  them  in  the  class  with  those  above  guarantee.  On  this  basis 
a  little  over  one-third  of  the  forty-nine  guaranteed  samples  were 
therefore  not  within  5  per  cent,  of  the  guaranteed  amount  of  total 
phenols. 

Extended  comment  on  these  results  is  unnecessary.  It  seems  evi- 
dent that  the  manufacturers  of  the  dips  which  were  found  to  be 
below  guarantee  had  no  extended  knowledge  of  the  composition  of 
their  products. 


PHENOLIC   INSECTICIDES    AND    FUNGICIDES  365 

Table  7 
These  preparations  may  be  said  to  be  fairly  satisfactory  in  con- 
forming to  the  guarantee.  Where  variations  occurred,  they  were  not 
usually  great.  With  one  or  two  exceptions  the  discrepancies  may  be 
accounted  for  by  the  cresylic  acid  used  in  making  up  the  compound. 
For  instance,  if  sample  number  1626,  Table  7,  had  been  made  up  from 
a  cresylic  acid  similar  to  sample  number  2571,  Table  2,  using  50  per 
cent,  of  this  acid  supposed  to  be  100  per  cent,  pure,  the  resultant  com- 
pound would  upon  analysis  show  only  46.74  per  cent,  total  phenols. 
This  may  be  remedied  by  a  more  thorough  knowledge  of  the  raw 
materials  that  go  to  make  up  the  finished  product. 

Table  8 
One  sample  only  of  cresylic  ointment  was  taken  by  the  inspectors. 
This  sample  appeared  to  be  a  satisfactory  product  although  no  state- 
ment was  made  of  the  per  cent,  of  its  active  ingredients. 

Table  9 
Very  little  attention  was  given  to  examination  of  the  powders. 
Those  samples  examined  appear  to  be  scarcely  worthy  of  the  name. 

WHO  IS  TO  BLAME? 

Those  manufacturers  and  dealers  whose  wares  are  shown  to  be 
dependable  are  to  be  congratulated.  The  others  are  not  accused  of 
willfully  making  or  selling  low-grade  or  non-standard  products,  but 
it  appears  that  material  often  has  been  guaranteed  and  sold  with  but 
slight  knowledge  of  its  composition. 

The  fault  does  not  lie  entirely  with  the  dealers,  but  the  blame 
must  be  shared  with  the  producers  in  other  states  who  have  shown 
hesitancy  in  giving  specific  guarantees  for  their  output;  if  a  guar- 
antee has  been  given,  it  may  not  have  had  very  close  relationship  to 
facts. 

An  instance  came  to  the  notice  of  the  office,  where  the  manufac- 
turer of  a  carbolic  dip  had  been  in  difficulty  with  certain  officials  in 
charge  of  the  enforcement  of  an  insecticide  law,  concerning  the 
phenolic  content  of  his  dip.  He  had  made  up  his  dip  with  a  coal-tar 
creosote  guaranteed  to  him  to  contain  a  high  percentage  of  phenols 
and  had  calculated  the  phenolic  content  of  the  finished  dip  upon  the 
basis  of  the  guarantee.  Analysis  showed  his  product  to  be  far  short 
of  the  supposed  amount  of  phenols.  Investigation  disclosed  the  fact 
that  different  shipments  of  the  creosote  he  was  using  varied  greatly. 


366  UNIVERSITY    OF    CALIFORNIA — EXPERIMENT    STATION 

An  analysis  of  a  sample  of  one  shipment  showed  20  per  cent,  less 
phenols  than  was  claimed. 

It  is  therefore  only  a  matter  of  course  that  this  manufacturer  of 
sheep  dip  could  not  make  a  standard  product  without  first  having 
analyzed  each  separate  lot  of  raw  materials  or  having  purchased  from 
firms  whose  guarantees  are  reliable. 

This  manufacturer  was  legally  responsible  for  the  composition  of 
his  products,  morally  the  responsibility  must  be  largely  shared  by 
the  producer  of  the  raw  material.  Circumstances  of  this  kind  will 
continue  to  occur  as  long  as  the  producers  of  raw  materials  do  not 
furnish  a  standard  and  dependable  article  to  their  distributors. 


A  BACKWARD  STEP  IN  INSECTICIDE  LEGISLATION 

It  seems  very  unfortunate  that  the  necessity  of  stating  the  per- 
centages of  active  ingredients  on  insecticide  labels  was  removed  by 
amendments  to  the  law.  This  appears  to  be  decidedly  a  backward 
step  in  insecticide  legislation.  It  lends  encouragement  to  the  pro- 
moter of  worthless  proprietary  preparations  and  the  sellers  of  hetero- 
geneous by-products  of  uncertain  composition.  It  greatly  impedes 
the  accomplishment  of  the  standardization  of  insecticides  and  fungi- 
cides which  is  so  much  to  be  desired  by  the  consumer  and  the  con- 
scientious producer. 

The  label  on  a  package  of  crude  carbolic  acid  may  now  venture  no 
more  information  than  that  the  article  is  crude;  but  how  crude  may 
only  be  a  matter  of  conjecture  unless  the  dealer  voluntarily  gives 
more  definite  information. 


PHENOLIC    INSECTICIDES    AND    FUNGICIDES  367 


Part  III 

METHODS  OF  EXAMINATION  AND  DESCRIPTION 
OF  APPARATUS 


QUANTITATIVE  METHODS 
Phenol 
The  percentage  of  absolute  phenol  in  samples  of  refined  phenol 
was  determined  by  Koppescharr's  method  as  modified  by  Allen.1  In 
brief  the  method  consists  in  precipitating  the  phenol  from  dilute 
aqueous  or  alcoholic  solution  with  bromine  in  the  form  of  tribrom- 
phenol. 

Cresol  and  Mixed  Phenols 

The  bromination  method  as  applied  to  phenol  is  not  suitable  for 
the  determination  of  cresol  for  the  reason  that  the  latter  does  not 
give  a  uniform  product  with  bromine.  As  previously  pointed  out, 
cresol  is  the  principal  phenolic  substance  or  tar  acid  usually  found  in 
the  crude  phenols  and  in  the  compounded  and  proprietary  remedies. 
Hence  some  other  method  must  be  used  for  the  determination  of  the 
phenols  in  the  above. 

The  method  of  Chapin2  was  adopted  as  being  the  best  available 
one  for  this  purpose.  The  method  is  equally  applicable  to  cresols, 
crude  phenols,  and  to  the  larger  proportion  of  the  compounded  and 
proprietary  remedies.  The  amount  of  the  sample  taken  for  analysis 
must  of  course  be  varied  so  that  the  volume  of  phenols  will  not  exceed 
the  capacity  of  the  measuring  tube.  Slight  modifications  are  neces- 
sary in  the  preliminary  treatment  of  some  of  the  materials  before 
distillation. 

Complete  Examination 

Those  who  may  be  interested  in  the  methods  for  a  complete  ex- 
amination of  phenolic  insecticides  and  fungicides  will  be  introduced 
to  the  literature  on  the  subject  by  looking  up  the  references  cited 
throughout  the  text.     Particular  reference  may  be  made  to  the  fol- 

1  Sutton,  Volumetric  Analysis,  10th  edition,  p.  415. 

2  U.  S.  Dept.  Agr.,  Bur.  Animal  Ind.,  Bull.  107,  1908. 


368  UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 

lowing  publications,  in  which  are  given  the  most  important  methods 
in  use  by  the  Government :  U.  S.  Department  of  Agriculture,  Bureau 
of  Animal  Industry,  Bulletins  100  and  107  and  Circular  167 ;  Forest 
Service,  Circulars  112,  191,  and  206 ;  Treasury  Department,  Public 
Health  and  Marine-Hospital  Service  of  the  U.  S.,  Hygienic  Labora 
tory,  Bulletin  82. 

QUALITATIVE  TESTS 
Eosin 

Rosin  may  be  easily  detected  by  applying  the  Liebermann-Storch 
test3  to  the  original  material. 

The  test  as  applied  in  the  Insecticide  Laboratory  is  as  follows:  A 
glass  rod  is  dipped  into  the  sample  to  be  tested  and  several  smears 
of  varying  quantities  of  the  material  are  made  on  a  white  porcelain 
test  plate ;  two  or  three  drops  of  acetic  anhydride  are  added  to  each 
smear  and  lastly  a  drop  of  concentrated  sulfuric  acid.  If  rosin,  rosin 
oil,  or  pine-tar  is  present  a  peculiar  fugitive  violet  or  purple  color 
appears  on  the  plate. 

Very  often  the  test  shows  up  better  when  made  upon  the  smallest 
trace  of  the  material.  The  most  desirable  quantity  to  produce  the 
characteristic  test  seems  to  vary  with  11k1  character  of  the  sample.  The 
test  therefore  is  made  upon  different  quantities  of  the  material  and 
there  is  usually  one  or  two  spots  which  show  up  more  distinctly  than 
the  rest. 

As  pointed  out  by  Chapin,  the  character  of  the  soap  employed  in 
making  a  dip  may  be  judged  by  observing  the  residue  in  the  flask 
after  the  first  distillation  in  a  current  of  steam.  The  author  found  it 
convenient  for  this  purpose  to  pour  the  residue  into  a  large  volume  of 
cold  water.  The  residue  from  a  straight  rosin  soap  immediately 
granulates  into  solid  particles  of  nearly  pure  rosin,  while  the  residue 
from  a  mixed  rosin  and  fatty  or  oily  soap  will  be  a  semi-solid,  a  thick 
or  thin  liquid,  depending  upon  the  nature  and  proportions  of  the 
soap  acids  present. 

Behavior  with  Water 

Unknown  liquids  are  very  simply  classified  into  emulsifiable,  non- 
emulsifiable,  and  soluble  by  stirring  a  small  quantity  of  the  sample 
with  water.  Some  idea  of  the  excess  alkalinity  of  the  emulsifiable  and 
soluble  compounds  may  be  gained  by  testing  at  this  point  with  litmus 
paper. 


•-*  U.  S.  Dept    of  Agr.,  Bur.  Chem.,  Bull.  109,  Revised,  p.  13. 


PHENOLIC    INSECTICIDES    AND    FUNGICIDES  369 

Nitrobenzene  or  Oil  of  Mirbane 

This  substance  may  be  identified  by  first  converting  it  into  aniline 
and  then  applying  the  well-known  phenylisocyanide  test. 

The  procedure  adopted  for  the  identification  of  nitro-benzene  in 
kerosene  solution  is  as  follows:  The  nitro-benzene  is  extracted  from 
the  kerosene  by  shaking  with  alcohol.  The  alcohol  is  evaporated  off 
and  the  nitro-benzene  converted  into  aniline  hydrochloride  by  adding 
a  pinch  of  zinc  powder  and  a  few  cubic  centimeters  of  concentrated 
hydrochloric  acid  and  warming.  The  acid  solution  is  filtered  and  to 
the  filtrate  is  added  alcoholic  potash  and  a  few  drops  of  chloroform. 
The  characteristic  odor  of  phenylisocyanide  is  easily  recognized  upon 
warming  the  mixture. 

SULFONATION   TEST* 

Hydrocarbons  of  the  benzene  series  may  be  distinguished  from 
those  of  the  paraffin  series  by  the  fact  that  the  former  are  acted  upon 
by  hot  concentrated  sulfuric  acid  forming  water-soluble  compounds, 
while  those  of  the  paraffin  series  are  unaffected  by  this  treatment. 
The  test  is  not  strictly  quantitative  but  does  give  a  very  good  indica- 
tion of  the  nature  and  source  of  an  oil. 

Dimethyl  Sulfate  Test5 

This  test  is  somewhat  simpler  than  the  preceding,  but  has  the  same 
end  in  view,  viz. :  to  determine  whether  the  sample  is  of  coal-tar  origin 
or  whether  it  is  in  part  or  wholly  derived  from  oil-gas-tar  or  tars  of 
other  origin,  or  is  mixed  with  petroleum  oils. 

APPAEATUS 

With  the  exception  of  the  phenol  measuring  tube,  the  apparatus 
necessary  for  performing  an  analysis  by  the  methods  herein  referred 
to  are  to  be  found  in  any  well-equipped  laboratory  or  can  be  pro- 
cured from  the  stock  of  the  chemical  supply  houses  on  short  notice. 
The  phenol  measuring  tube  is  easily  made  and  calibrated  by  a  glass 
blower.  The  determination  of  the  phenols  can  be  made  by  any  one 
who  is  at  all  familiar  with  laboratory  technique.  The  processes  are 
somewhat  tedious,  however,  and  when  a  number  of  analyses  are  to 
be  made,  the  work  becomes  burdensome.  In  order  to  facilitate  the 
work,  some  new  apparatus  has  been  developed  in  the  Insecticide  Lab- 
oratory, a  description  of  which  may  be  of  interest  to  those  who  have 


4  Batemann,  U.  S.  Dept.  of  Agr.,  Forest  Service,  Circular  112;   also  Circulars 
191  and  206. 

•r>  Chapin,  IT.  S.  Dept.  of  Agr.,  Bur.  Animal  Ind.,  Circular  167. 


370 


UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 


a  number  of  analyses  to  make  as  a  matter  of  routine.  The  new  ap- 
paratus described  is  a  steam  distillation  battery,  a  mechanical  shaker, 
and  a  small  device  for  holding  flasks  in  the  water  bath.  Illustrations 
are  given,  however,  showing  each  step  in  Chapin's  method  for  the 
determination  of  total  phenols. 

In  order  to  conduct  the  analyses  without  delays  several  samples 
were  carried  through  at  one  time,  the  various  processes  being  usually 
conducted  in  sets  of  either  three  or  six,  depending  upon  the  time  con- 
sumed and  the  nature  of  the  process.    The  number  of  samples  treated 


Fiji'.  1. — Steam  Distillation  Battery 


simultaneously   in   the   different   operations   may   be   ascertained   by 
reference  to  the  cuts  showing  the  different  steps. 


The  Steam  Distillation  Battery 
Chapin's  method  involves  the  distillation  of  the  acidified  sample 
in  a  current  of  steam  until  the  distillate  amounts  to  at  least  800  cc. 
This  operation  usually  requires  considerably  more  than  an  hour's 
time.  The  apparatus  shown  in  figure  1  has  been  arranged  and  found 
to  be  of  great  assistance  in  the  determination  of  the  phenols  by  this 
method.     Incidentally  it  is  also  used  whenever  a  process  calls  for 


PHENOLIC   INSECTICIDES   AND    FUNGICIDES  371 

steam  distillation,  being  especially  useful  in  the  determination  of 
nicotine. 

The  fixed  support  for  the  condensers  and  distillation  flasks  was 
suggested  in  an  article  by  Crossley.6  The  idea  adapted  to  the  needs 
of  this  laboratory  is  as  follows :  The  support  is  fastened  to  the  bench 
by  means  of  foot  plates  and  screws.  To  increase  its  rigidity,  the 
upper  part  of  the  frame  is  fastened  by  braces  to  the  wall.  Ordinary 
%-inch  gas  pipe  and  the  necessary  couplings  were  selected  as  suitable 
materials  for  its  construction.  The  rack  consists  of:  First,  two  up- 
rights placed  50  inches  apart.  These  uprights  are  made  up  of  a 
piece  of  pipe  16  inches  long,  screwed  into  a  foot  plate  at  one  end  and 
into  a  T  at  the  other,  there  being  also  screwed  into  this  T  a  longer 
pipe  of  24  inches  surmounted  by  a  three-way  coupling  to  accommo- 
date the  upper  horizontal  pipe  and  the  wall  brace.  (The  upright  at 
the  right  is  not  shown  in  the  cut.)  Second,  two  horizontal  pipes  50 
inches  long,  one  connecting  the  upper  ends  of  the  two  uprights,  the 
other,  connected  to  the  T's  in  the  uprights.  Four  T's  are  inserted 
into  each  horizontal  pipe  at  corresponding  intervals  of  10  inches  to 
receive  the  shorter  verticals.  Third,  connecting  the  opposite  T's  in 
the  two  horizontal  pipes  are  four  vertical  pipes  24  inches  in  length. 

To  the  completed  rack  can  be  attached  the  required  flasks,  con- 
densers, and  other  apparatus  by  means  of  the  ordinary  clamps  and 
clamp  fasteners.  The  water  supply  for  the  condensers  is  brought  up 
to  the  rack  in  a  horizontal  pipe  running  the  length  of  the  rack,  at- 
tached to  it  by  means  of  clamp  fasteners,  and  having  pet-cocks  at 
convenient  intervals.  A  drain  pipe  is  also  supported  on  the  rack  in 
the  same  way. 

The  supply  of  steam  is  generated  in  a  copper  tank  of  about  four 
gallons  capacity  provided  with  a  water-glass  marked  off  at  intervals 
to  show  the  amount  of  water  in  the  tank.  A  glass  tube  about  three 
feet  in  length  is  inserted  through  a  stopper  held  in  an  opening  in  the 
top  of  the  boiler  and  extends  nearly  to  the  bottom  of  the  boiler.  The 
function  of  this  tube  is  to  act  as  a  safety  valve  and  to  give  a  general 
idea  of  the  pressure  in  the  apparatus  by  observing  the  height  of  the 
water  in  the  tube.  The  steam  is  conducted  along  the  upper  length 
of  the  rack  in  a  i^-inch  pipe  insulated  by  about  %  inch  of  asbestos 
paper  which  is  applied  wet  in  thin  layers  and  subsequently  dried.  To 
the  outer  end  of  the  steam  pipe  is  attached  an  elbow  and  a  pipe  lead- 
ing to  the  drain.  At  this  end  there  is  also  a  valve  which  is  useful  for 
draining  the  condensed  steam  from  the  pipe  when  the  apparatus  is 

6  A  Simple  Form  of  Laboratory  Support.  T.  Linsey  Crossley.  Journ.  Ind. 
Eng.  Chem.,  Vol.  4,  No.  11,  p.  846. 


372  UNIVERSITY   OF    CALIFORNIA EXPERIMENT    STATION 

being  warmed  up  and  is  also  of  use  in  relieving  the  pressure  in  the 
apparatus  whenever  necessary.  The  steam  is  distributed  from  this 
pipe  to  the  distillation  flasks  through  pet-cocks  placed  at  intervals  of 
ten  inches.  Connection  is  made  between  the  pet-cocks  and  the  glass 
tubes  which  conduct  the  steam  into  the  flasks  by  means  of  short  pieces 
of  rubber  tubing. 

The  arrangement  described  above  eliminates  many  sources  of  in- 
convenience often  encountered  in  the  usual  manner  of  conducting 
steam  distillations.  The  use  of  rubber  tubing  is  reduced  to  a  mini- 
mum, the  short  pieces  used  being  easily  replaced  when  necessary  at 
slight  expense.  The  capacity  of  the  burner  employed  was  sufficient 
for  three  simultaneous  distillations  only,  but  the  fourth  condenser 
was  found  to  be  of  convenience  in  allowing  a  sample  to  be  prepared 
ready  for  analysis  and  the  flasks,  etc.,  to  be  attached  to  it  ready  for 
turning  in  the  steam  whenever  one  distillation  has  been  completed. 

The  Mechanical  Shaker 

A  part  of  Chapin's  method  that  requires  no  small  amount  of  both 
manual  labor  and  time  is  the  shaking  of  the  large  separatory  funnels 
five  minutes,  three  times,  at  intervals  of  half  an  hour.  In  the  analysis 
of  a  few  occasional  samples  this  objection  is  not  serious,  but  when  a 
considerable  number  of  samples  are  to  be  run  through  as  a  matter 
of  daily  routine,  the  busy  analyst  must  seek  some  device  to  overcome 
this  difficulty.  Search  was  made  in  the  catalogs  of  the  chemical  sup- 
ply houses  and  no  shaker  was  found  listed  which  gave  promise  of 
being  entirely  satisfactory  for  the  purpose  in  view.  The  author  had 
previously  used  a  "home-made"  mechanical  shaker  in  the  cereal  lab- 
oratory of  the  University  while  working  under  the  direction  of  Dr. 
G.  W.  Shaw.  This  shaker  was  so  readily  adaptable  to  hold  a  great 
variety  of  glassware  and  could  be  constructed  sufficiently  strong  for 
most  kinds  of  work,  that  it  was  thought  a  similar  apparatus  could  be 
made  to  accommodate  a  number  of  the  large  separatory  funnels  used 
in  the  process  under  discussion. 

Mr.  E.  J.  Hoff,  Mechanician,  U.  S.  Irrigation  Investigations,  kindly 
agreed  to  construct  a  shaker  similar  to  the  one  in  use  in  the  cereal 
laboratory,  but  of  larger  capacity,  and  offered  many  valuable  sug- 
gestions in  its  construction.  After  the  construction  of  the  shaker 
many  contrivances  were  made  by  the  author  and  promptly  discarded 
before  a  suitable  manner  of  holding  the  funnels  in  the  box  was  found. 
Simple  devices  were  finally  evolved,  however,  which  permitted  the 
easy  insertion  and  withdrawal  of  the  funnels  and  held  them  securely 


PHENOLIC   INSECTICIDES    AND    FUNGICIDES  373 

in  place  without  the  use  of  screws,  springs,  or  clamps.  The  shaker 
which  has  given  excellent  service  in  the  Insecticide  Laboratory  for 
some  three  years  is  illustrated  in  Figure  2.  It  is  represented  as  carry- 
ing a  load  of  six  two-liter  separatory  funnels,  each  containing  800  cc. 
of  the  distillate  from  a  phenol  determination,  200  grams  of  salt,  and 
150  cc.  of  benzene  for  the  extraction  of  the  phenols  from  the  brine. 

The  apparatus  consists  of :  First,  sl  plain  well-made  box,  5  X  16  X 
30  inches  inside  dimensions.  This  box  is  suspended  at  one  end  by 
means  of  two  chains  attached  to  the  corners.  The  other  end  of  the 
box  is  supported  from  the  bench  by  means  of  an  iron  bar,  %  inch 
thick,  1  inch  wide,  bent  twice  at  right  angles.     The  bar  is  about  37 


Fig.  2. — Mechanical  Shaker,  general  view  with  load. 

inches  long  and  the  bends  are  made  about  9%  inches  from  either  end, 
making  two  legs  of  equal  length  and  a  longer  length  capable  of  span- 
ning the  outside  width  of  the  box.  The  longer  length  is  laid  flat  upon 
the  bench  and  secured  thereto  by  means  of  lag-screws  passing  through 
loosely  fitting  holes  in  the  bar.  The  lag-screws  are  not  entirely 
screwed  down  in  order  to  allow  the  bar  to  be  rocked  back  and  forth. 
The  bench  is  protected  from  wear  by  iron  washers  around  the  screws 
and  beneath  the  bar.  The  free  ends  of  the  legs  are  hinged  to  vertical 
plates  attached  to  the  two  corners  of  the  box,  extending  about  an  inch 
below  the  bottom  thereof.  Second,  a  %  horsepower  motor.  Third, 
belts  and  pulleys  for  the  transmission  of  power  and  reduction  of 
speed,  and  a  crank  for  converting  the  circular  motion  of  the  motor 
into  vibratory  motion.     This  can  be  accomplished  by  anyone  of  a 


374  UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 

mechanical  turn  of  mind  and  the  arrangements  would  be  greatly 
different  to  meet  the  various  requirements  of  the  work  in  hand  and 
the  convenient  location  of  motor  and  shaker.  It  would  be  a  waste  of 
space  to  describe  these  contrivances  other  than  to  state  that  the  speed 
of  the  motor  has  been  geared  down  to  produce  a  speed  in  the  shaker 
of  120  to  130  vibrations  per  minute,  and  the  crank  so  arranged  that 
the  length  of  vibration  is  3  inches. 

The  criticism  that  may  be  made  to  many  of  the  mechanical  shakers 
that  are  offered  for  sale  is  that  the  motions  produced  are  too  regular 
and  simple  to  ensure  a  thorough  contact  of  two  immiscible  liquids. 
The  particular  point  of  advantage  claimed  for  the  one  described 
above  is  that  it  produces  a  variety  of  motions  abundantly  sufficient  to 
churn  the  two  liquids  into  intimate  contact.  One  end  of  the  box 
being  supported  from  below  and  the  other  end  being  suspended,  it 


Fig.  3. — Device  for  holding  steins  of  separatory  funnels  in  place  in  the  shaker. 

is  evident  that  any  point  in  one  end  of  the  box  must  travel  through 
an  arc  the  reverse  of  any  point  at  the  opposite  end  during  an  oscilla- 
tion. The  manner  of  fastening  the  iron  box  support  to  the  bench  also 
adds  to  the  complexity  of  motion.  When  the  legs  of  the  bar  are  in 
a  vertical  position  the  horizontal  part  lies  flat  upon  the  bench,  but  is 
partly  turned  on  edge  as  the  apparatus  is  moved  back  and  forth.  The 
corresponding  end  of  the  box  is  therefore  slightly  raised  and  lowered 
during  each  oscillation. 

The  stems  of  the  separatory  funnels  are  held  in  place  in  the  box 
of  the  shaker  by  the  device  which  is  separately  shown  in  Figure  3. 
This  rack  fits  snugly  into  the  bottom  of  the  box  and  is  removable  to 
permit  the  insertion  of  holding  arrangements  for  other  glassware. 
The  wooden  strips  for  the  slots  are  placed  iy2  inches  apart  and  pieces 
of  %-inch  ordinary  white  rubber  tubing  are  tacked  along  the  inner 
sides  of  the  slots.     (The  block  supporting  the  funnel  in  the  cut  is  not 


PHENOLIC    INSECTICIDES    AND    FUNGICIDES 


375 


Fig.  4. — Detail  of  the  construction  of  saddle  for  holding  the  necks  of 
the  separatory  funnels  in  place  in  the  shaker. 

a  part  of  the  rack,  but  is  merely  present  to  hold  the  funnel  in  place 
while  being  photographed.)  In  practice  the  necks  of  the  funnels  are 
held  in  place  by  means  of  saddles  placed  at  intervals  along  the  edges 
of  the  box,  details  of  which  are  indicated  in  Figure  4.  These  saddles 
are  made  by  screwing  pairs  of  right-angled  hooks  into  the  edge 
of  the  box,  each  hook  being  two  inches  distant  from  its  mate.  The 
ends  of  the  hooks  are  slipped  through  holes  cut  in  the  side  of  a  piece 
of  rubber  tubing  of  sufficient  length  to  allow  it  to  sag  between  the 
pairs  of  hooks  and  rest  upon  the  edge  of  the  box.  This  device  offers 
a  firm  rest  to  the  necks  of  the  funnels  and  holds  them  with  surpris- 


Fig.  5. — Rack  holding  six  large  separatory  funnels  during  an  interval 
between  the  three  extractions  with  benzene. 


376 


UNIVERSITY    OF    CALIFORNIA EXPERIMENT    STATION 


ing  tenacity,  from  being  thrown  out  by  the  motion  of  the  shaker.  The 
horizontal  slots  (Figure  3)  care  for  the  other  ends  of  the  funnels  with 
equal  efficiency.  The  slot  arrangement  for  holding  the  stems  allows 
for  a  considerable  variation  in  the  length  and  size  of  the  stems  as  is 
usually  found  in  purchasing  different  lots. 

Water  Bath  and  Condenser 
Figure  6  represents  the  water  bath  and  condenser  used  in  distilling 
off  the  excess  benzene  used  in  the  extraction  of  the  phenols.     Special 

i  i 


Fig..  6. — Distilling  off  the  excess  of  benzene  accumulated  in  the 
three  extractions. 


mention  is  made  of  this  illustration  to  call  attention  to  the  location  of 
the  condenser  on  the  edge  of  the  table,  the  location  of  the  receiving 
flasks  below  the  table,  and  the  manner  of  holding  the  flasks  in  the  water 
bath.  Danger  of  fire  through  breakage  of  the  receiving  flasks,  or  un- 
condensed  vapor  being  carried  to  the  flame,  is  greatly  lessened  by 
placing  the  receiving  flasks  below  the  table. 


PHENOLIC    INSECTICIDES    AND    FUNGICIDES 


377 


Device  for  Holding  Flasks  in  Place  in  a  Water  Bath 
Figure  7  pictures  a  500  cc.  Erlenmeyer  flask  with  its  dress  on, 
ready  to  be  placed  in  a  water  bath.  The  flask  is  dressed  for  the  oc- 
casion by  slipping  over  its  neck  three  rings  of  the  water  bath ;  follow- 
ing the  smaller  ring  there  comes  a  hollow  truncated  cone,  whose  lower 
diameter  is  of  a  size  to  fit  the  groove  of  the  smaller  ring,  the  upper 
diameter  being  just  large  enough  to  pass  over  the  lip  of  the  flask.    The 


Fig.  7. — A  convenient  arrangement  for  holding  flasks  in  place  in  a  water  bath. 


cone  (shown  at  the  right  of  the  cut)  is  of  the  proper  height  to  allow 
an  ordinary  wooden  test  tube  holder  to  snap  around  the  neck  of  the 
flask  below  the  lip.  The  weight  of  the  flask  and  contents  can  thus  be 
supported  upon  the  rings  of  the  bath  and  the  necessity  of  the  usual 
"forest"  of  ring-stands,  clamps  and  attachments  is  entirely  removed. 
The  author  acknowledges  the  valuable  assistance  of  his  associate, 
Mr.  M.  R.  Miller,  who  made  the  photographs  used  to  illustrate  the  ap- 
paratus shown  in  this  part  of  the  bulletin. 


378  UNIVERSITY   OF    CALIFORNIA — EXPERIMENT    STATION 


Fig.  8. — Tne  transier  oi  tiie  pnenols  tioin  aqueous  to  benzene  solution 
after  distilling  off  the  excess  of  benzene. 


Fig.  9. — The  final  measurement  of  the  phenols  in  the  tubes  designed  by 
Chapin.  The  two  tubes  at  the  right  of  the  cut  are  shown  containing  a  measured 
volume  of  sodium  hydroxide  solution  and  one  or  two  cc.  of  benzene,  ready  to 
receive  the  phenols  for  final  measurement.) 


PHENOLIC   INSECTICIDES   AND    PUNGIC1DKS  379 


INDEX  OF  SAMPLES 

The  author's  classification  of  the  samples  herein  listed  may  be 
ascertained  by  referring  to  the  heading  of  the  table  in  which  the 
analysis  of  the  sample  is  listed.  The  headings  of  the  tables  have  been 
made  to  correspond  to  the  scheme  of  classification  shown  in  part  I. 


Acid,  Carbolic  

Acid,  Carbolic,  Crude  

Acid,   Cresylic 

A.  D.  S.  Kresano  

A  &  M  Lice  Killer  

Alber's  Liquid  Lice  Killer  

Braucco   Cresol  

Cabot's  Sulpho-Napthol  

Carbolated  Lime  

Carbolic  Acid,  Crude  

Carbolic  Acid    

Carbolic  Powders  

Carbolic  Powder,  Compound  ... 

Carbo-Napthol  

Carbo  Negus  

Ceoline  Dog  Wash  

Chloro-Naptholeum 

Chloro-Naptholeum  Dip    

Clayton's  Mange  Eemedy  

Coal-tar  Creosote  

Conkey's  Fly  Knocker  

Conkey's  Lice  Liquid  

"C  N"  Disinfectant  

Cow-Ease    

Cre-aseptol  

Cre-aseptol   

Creo-Carbo 

Oreofect    

Creofenol  Dip  

Creo  Fenol  Sheep  Dip 

Creol  Dip  

Creolin-Pearson 

Creophene  

Creosote,   Coal-tar    

Creosote  Oil  

Creosozone    

Creosozone  Liquid  Lice  Killer 

Cresylic  Acid    

Cresylic   Ointment   


Sample  No. 

Tab 

1 

3 

2 

2165 

6 

2547 

4 

004,  2603 

4 

523 

2 

66 

6 

25 

9 

3 



1 

9 

1448 

9 

722 

6 

86 

6 

35 

6 

712 

6 

713 

6 

84 

4 

3 

237 

4 

496 

6 

182 

6 

274 

4 

1022 

7 

2594 

5 

212 

4 

59 

6 

1132 

6 

3224 

6 

2584 

6 

121 

6 

435 

6 

3 

3 

155 

4 

1503 

4 

2 

233 

8 

380 


UNIVERSITY    OP    CALIFORNIA EXPERIMENT    STATION 


Cresylol  

Cresol  Compound,  Solution   

Cresolene    

Cresoleum   

Cresolis  Compound  

Cresolite   Sheep   Dip   

Cresol    

Crude  Carbolic  Acid    

Dips   

Disinfectants  

Dog  Wash,  Ceolene  

Emulsion   Disinfectant   

Flyfoe    

Flyo-Curo    

Fly  Keep  Off  

Fornolice     

Fuller's  Carbolic — 

Hop  Spray  

Poultry  Spray  

Kose  &  Vine  Spray  

Sheep  Dip  &  Cattle  Wash  

Tree  Spray  

Germfoe    

Germ  Killer,  Dr.  David  Roberts'  

Germo    

Germo-Carbolene     

Glover's  Imperial  Mange  Remedy  

Gold  Coin  Lice  Killer  

Hess  Dip  and  Disinfectant,  Dr 

Ideal  Stock  Dip  

Imperial  Sheep  Dip  

Kasol  

Kill-Bug   

Koltarcre 

Kresano,  A.  D.  S 

Kreso    

Kreso  Dip  No.  1 

Lee's  Lice  Killer  163, 

Lee's  Sheep  Dip  

Lice  Killers  

Lice  Liquid,  Conkey's  

Lice  Paint   

Liquor  Cresolis  Compositus  

Liq.  Cresolis  Comp.  (Kasol)   

Little's  Improved  Fluid  Dip  

Little's  Improved  Fluid  Dip  

Little's  Sheep  Dip  

Little's  Soluble  Phenyle  456, 

Little's  Special  Fluid  Dip  


Sample  No. 

Table 

546,  2508 

6 

1626 

7 

493 

6 

3376 

6 

3256 

7 

1114,  3377 

6 

2 

3 

5,  6 

4,  5,  6,  7 

35 

6 

2653 

6 

1063,  2620 

4 

238 

4 

275 

4 

2104 

4 

1255,  2177 

6 

1257,  2179 

6 

1254,  2178 

6 

1256,  2180 

6 

1253,  2176 

6 

1061,  2610 

6 

215 

5 

4 

1068,  2622 

6 

53 

4 

263 

4 

197 

6 

2375 

5 

1074,  2556 

6 

2094 

7 

714 

4 

2624 

6 

2165 

6 

186 

6 

422 

6 

1002,  1515 

4 

1520 

6 

4,  6 

496 

6 

2246 

4 

3386 

7 

2094 

7 

717 

5 

827 

10 

2043 

6 

719,  2248 

6 

718 

6 

PHENOLIC   INSECTICIDES   AND    FUNGICIDES  381 

Sample  No.  Table 

Lysol    88  7 

Mange  Cure,  Spratt's  Eczema  and  21  4 

Mange  Remedy,  Clayton's  84  4 

Mange  Eemedy,  Glover's  Imperial    53  4 

Mange  Remedy,  Todco    1145,  2196  '  6 

Mealy  Bug  Spray,  Sun  2633  6 

Merton's  Phenolene  450,  2163  6 

No-Fly     253  4 

Noxicide   497  6 

Ointment,  Cresylic  233  8 

Orwood  Lice  Killer  901  4 

Owl  Drug  Co.  Dip  1137  6 

Owl's  Soluble  Phenyl  1138,  3203  6 

Palo  Alto  Sheep  Dip  and  Disinfectant  2250  6 

Phenocide     1  6 

Phenolene,  Merton's  450,  2163  6 

Phenol  1 

Phenol  Sodique  70  7 

Phenyl,  The  Owl's  Soluble  1138,  3203  6 

Phenyl,  Shumate's  1271,  3292  6 

Phenyle,  Little's  Soluble  456,     719,  2248  6 

Pine-tar    542  10 

Red  Cross  Sanitary  Fluid  89  6 

Roberts'  Germ  Killer,  Dr.  David  215  5 

Sanax  Disinfecting  Fluid  200  6 

Sanford's  Lice  Killer  446  4 

San-i-tin  or  Sheep  Dip  2082  6 

Scalefoe    2611  4 

Security  Carbolized  Disinfectant  259,  2062  6 

77  Dip.     Disinfecting  Fluid  2673  6 

S  &  G  Chicken  Dip  3254  6 

S  &  G  Chicken  Dip  and  Lice  Killer  1239  6 

S  &  G  Lice  Killer 1237  6 

S  &  G  Poultry  Lice  Killer   273  6 

S  &  G  Sheep  Dip  1236,  3253  6 

Sheep  Dips  5,  6 

Shumate's  Phenyl    1271,  3292  6 

Spratt's  Eczema  and  Mange  Cure  21  4 

Stayco  Sheep  Dip  1011  5 

Stockmen's  Antiseptic  Dip  261  6 

Sturtevant  Lice  Paint    2246  4 

Sulpho-Napthol,  Cabot's    66  6 

Sun  Mealy  Bug  Spray  2633  6 

Tar,  Pine    542  10 

Todco  Mange  Remedy  1145,  2196  6 

Users'  Samples  10 

Veritable  Phenol-Baboeuf  71  7 

W.  C.  Lice  Killer  1059  4 

West  Coast  Lice  Killer  2615  4 

Zenoleum    194  6 


STATION  PUBLICATIONS  AVAILABLE  FOR  DISTRIBUTION 


Appendix  to  Viticultural 


REPORTS 
1897.      Resistant  Vines,  their  Selection,   Adaptation,   and  Grafting. 
Report  for   1896. 

1902.  Report  of  the  Agricultural  Experiment   Station   for   1898-1901. 

1903.  Report  of  the  Agricultural   Experiment   Station   for   1901-03. 

1904.  Twenty-second  Report  of  the  Agricultural  Experiment   Station  for   1903-04. 

1914.  Report  of  the  College  of  Agriculture  and  the  Agricultural   Experiment   Station,   July, 

1913-June,  1914. 

1915.  Report  of  the  College  of  Agriculture   and  the  Agricultural   Experiment   Station,   July, 

1914-June,  1915. 

BULLETINS 
No. 
246 
248 


No. 
168. 

169. 
174. 
178. 
184. 

185. 

195. 
203. 

207. 
208. 
212. 
213. 
216. 


220. 
225. 
227. 
230. 
234. 
241. 
242. 
244. 


Observations  on  Some  Vine  Diseases 
in  Sonoma  Count/. 

Tolerance  of  the  Sugar  Beet  for  Alkali. 

A  New  Wine-Cooling  Machine. 

Mosquito   Control. 

Report  of  the  Plant  Pathologist  to 
July  1,   1906. 

Report  of  Progress  in  Cereal  Investi- 
gations. 

The  California  Grape  Root-worm. 

Report  of  the  Plant  Pathologist  to 
July  1,   1909. 

The  Control  of  the  Argentine  Ant. 

The  Late  Blight  of  Celery. 

California   White   Wheats. 

The  Principles  of  Wine-making. 

A  Progress  Report  upon  Soil  and 
Climatic  Factors  Influencing  the 
Composition  of  Wheat. 

Dosage  Tables. 

Tolerance  of  Eucalyptus  for  Alkali. 

Grape  Vinegar. 

Enological   Investigations. 

Red  Spiders  and  Mites  of  Citrus  Trees. 

Vine  Pruning  in  California.     Part  I. 

Humus  in  California  Soils. 

Utilization  of  Waste  Oranges. 


249. 
250. 
251. 


252. 
253. 

254. 
255. 
256. 
257. 
258. 
261. 

262. 

263. 
264. 
265. 
266. 

267. 
268. 
269. 


Vine  Pruning  in  California.     Part  II. 
The  Economic  Value  of  Pacific  Coast 

Kelps. 
Stock  Poisoning  Plants  of  California. 
The  Loquat. 

Utilization    of    the    Nitrogen    and    Or- 
ganic  Matter   in    Septic    and   Imhoff 

Tank  Sludges. 
Deterioration  of  Lumber. 
Irrigation   and   Soil   Conditions   in  the 

Sierra  Nevada  Foothills,  California. 
The  Avocado  in  California. 
The  Citricola  Scale. 
Value  of  Barley  for  Cows  fed  Alfalfa. 
New  Dosage  Tables  . 
Mealy  Bugs  of  Citrus  Trees. 
Melaxuma    of    the    Walnut,     "Juglans 

regia." 
Citrus    Diseases    of   Florida    and    Cuba 

compared  with  those  of  California. 
Size  Grade  for  Ripe  Olives. 
The  Calibration  of  the  Leakage  Meter. 
Cottony  Rot  of  Lemons  in  California. 
A  Spotting  of  Citrus  Fruits  Due  to  the 

Action  of  Oil  Liberated  from  the  Rind. 
Experiments  with  Stocks  for  Citrus. 
Growing  and  Grafting  Olive  Seedlings. 
Phenolic   Insecticides   and   Fungicides. 


No. 


CIRCULARS 

No. 


65.   The  California   Insecticide  Law. 

69.  The   Extermination   of   Morning-Glory. 

70.  Observations    on    the    Status    of    Corn 

Growing  in  California. 
76.   Hot  Room  Callusing. 
82.  The     Common     Ground     Squirrels     of 

California. 
100.   Pruning  Frosted  Citrus  Trees. 

106.  Directions  for  using  Anti-Hog-Cholera 

Serum. 

107.  Spraying  Walnut  Trees  for  Blight  and 

Aphis  Control. 

108.  Grape  Juice. 

109.  Community  or   Local   Extension   Work 

by  the  High  School  Agricultural  De- 
partment. 

110.  Green  Manuring  in  California. 

111.  The  Use  of  Lime  and  Gypsum  on  Cali- 

fornia Soils. 

113.  Correspondence  Courses  in  Agriculture. 

114.  Increasing  the  Duty  of  Water. 

115.  Grafting  Vinifera  Vineyards. 

117.  The    Selection    and    Cost    of    a    Small 

Pumping  Plant. 

118.  The  County  Farm  Bureau 

119.  Winery  Directions. 

121.  Some   Things    the    Prospective    Settler 

Should  Know. 

122.  The  Management  of   Strawberry   Soils 

in  Pajaro  Valley. 
124.   Alfalfa  Silage  for  Fattening  Steers. 


125. 
126. 
127. 
128. 
129. 
130. 
131. 
132. 

133. 
134. 
135. 
136. 
137. 
138. 
139. 


140. 


142. 

143. 

144. 
145. 

146. 

147. 
148. 
149. 


Aphids  on  Grain  and  Cantaloupes. 

Spraying  for  the  Grape  Leaf  Hopper. 

House  Fumigation. 

Insecticide  Formulas. 

The  Control  of  Citrus  Insects. 

Cabbage   Growing  in   California. 

Spraying  for  Control  of  Walnut  Aphis. 

When  to  Vaccinate  against  Hog 
Cholera. 

County  Farm  Advisor. 

Control  of  Raisin  Insects. 

Official  Tests  of  Dairy   Cows. 

Melilotus    Indica. 

Wood  Decay  in  Orchard  Trees. 

The  Silo  in  California  Agriculture. 

The  Generation  of  Hydrocyanic  Acid 
Gas  in  Fumigation  by  Portable  Ma- 
chines. 

The  Practical  Application  of  Improved 
Methods  of  Fermentation  in  Califor- 
nia Wineries  during  1913  and  1914. 

Standard  Insecticides  and  Fungicides 
versus    Secret   Preparations. 

Practical  and  Inexpensive  Poultry  Ap- 
pliances. 

Control  of  Grasshoppers  in  Imperial 
Valley. 

Oidium  or  Powdery  Mildew  of  the  Vine. 

Suggestions  to  Poultrymen  concerning 
Cbicken   Pox. 

Jellies  and  Marmalades  from  Citrus 
Fruits. 

Tomato  Growing  in  California. 

"Lungworms." 

Lawn  Making  in  California 


